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Theoretical investigations of structural, spectroscopic and electron collision

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 Molecular Physics
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Theoretical investigations of structural,

spectroscopic and electron collision data of
acetone

D. Prajapati, P. C. Vinodkumar, C. Limbachiya & M. Vinodkumar

To cite this article: D. Prajapati, P. C. Vinodkumar, C. Limbachiya & M. Vinodkumar (2021):

Theoretical investigations of structural, spectroscopic and electron collision data of acetone,
Molecular Physics, DOI: 10.1080/00268976.2021.1948124

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MOLECULAR PHYSICS e1948124
https://doi.org/10.1080/00268976.2021.1948124

RESEARCH ARTICLE

Theoretical investigations of structural, spectroscopic and electron collision data

of acetone
D. Prajapati a,b , P. C. Vinodkumar a , C. Limbachiya c and M. Vinodkumar d

a Department of Physics, Sardar Patel University, Vallabh Vidyanagar, India; b Shree M R Arts & Science College, Rajpipla, India; c Department of

Applied Physics, The M. S. University of Baroda, Vadodara, India; d Electronics Department, V.P. & R.P.T.P. Science College, Vallabh Vidyanagar,
India

ABSTRACT ARTICLE HISTORY

Comprehensive computational studies are carried out for the structural, spectroscopic and electron Received 14 April 2021
collision data of acetone. The time-dependent density functional theory (TDDFT) is employed to Accepted 20 June 2021
compute singlet and triplet vertical excitation energies and to determine their valence/Rydberg char- KEYWORDS
acter. Excellent correlation is obtained between the predicted spectral features with the available Excitation; resonance;
experimentally observed spectral features. We also report a detailed study on the e-acetone interac- electron impact collision;
tions for the comprehensive energy range starting from 0.1 to 5000 eV. We found a smooth matching ionisation; transport and rate
of R-matrix and SCOP data for total cross sections at 17 eV and hence are able to estimate the total coefficients
cross sections over such a wide energy range. Moreover, the study is augmented with additional
data on Eigenphase sum, differential cross sections (DCS), momentum transfer cross sections (MTCS),
electronic excitation cross-sections, symmetry decomposition of elastic cross sections, inelastic cross
sections, etc. Ionisation cross-sections are computed using Complex scattering Potential-ionisation
contribution (CSP-ic) and Binary Encounter Bethe (BEB) formalisms. Transport coefficients such as
mean free path, diffusion and mobility coefficients are calculated from the effective collision fre-
quency and the rate coefficients are estimated over a wide electron temperature range for elastic and
inelastic processes. Importantly, we have been able to identify new resonances (π ∗ ; σ ∗ and δ ∗ ) from
the present study. The theoretical data obtained here will be of great use in varieties of applications
involving acetone.

1. Introduction
Acetone is ubiquitous in the environment and is found in
a wide range of concentrations with varieties of applica-
tions. It is mainly used as a solvent, intermediate in chem-
ical production and the manufacture of explosives, poly-
carbonate resins and artificial fibres. Acetone is found in
almost every tissue and organ in the human body and
normally present as a metabolic component in human
breath, urine and blood [1]. Acetone has been detected
in variety of plants and foods [2–5]. Natural emissions
from certain tree species contain acetone vapour [6] and
another source is direct emission from the ocean [7].

CONTACT D. Prajapati dineshphy13@gmail.com Department of Physics, Sardar Patel University, Vallabh Vidyanagar 388 120, India

© 2021 Informa UK Limited, trading as Taylor & Francis Group

2 D. PRAJAPATI ET AL.
Pharmaceutical applications of acetone include use as an
intermediate and solvent for drugs, vitamins and cos-
metics [8]. It is used as an extraction solvent for fats
and oils and a precipitation agent in the purification of
starches and sugars [9]. Acetone at interstellar medium
was observed by Combes et al. [10,11] and upon the
first touchdown of the Philae lander on comet 67P’s sur-
face, the Cometary Sampling and Composition (COSAC)
detected for the first time on a comet [12,13]. Such
study of the chemical composition of comets provides key
information about the raw materials present in the early
solar system [14,15]. For more detailed study in all these
cases require reliable atomic and molecular cross sec-
tional data. In biological media, low energy electrons can
fragment molecules and lead to the formation of highly
reactive radicals and ions, which play an important role
in the dissociation of biomolecules and the production of
single and double-strand breaks in DNA [16–18]. Look-
ing into the diverse applications of acetone from interstel-
lar medium to metabolic activities, thus the present study
aims to provide extensive data on structural properties as
well as spectroscopic data along with low to high energy
electron collision data for acetone.
Experimentally, the total cross sections (TCS) for e-
acetone were measured by Szmytkowski et al. [19] in
the energy range 0.7 –400 eV and Kimura et al. [20]
in the energy range 1–700 eV, while Homem et al. [21]
and Pastega et al. [22] calculated TCS in the energy
range 1–500 eV and 2–1000 eV respectively. Differen-
tial cross sections (DCS), symmetry decomposed elastic
cross section for C2v point group were studied theoreti-
cally by Homem et al. [21] and Pastega et al. [22]. Ioni-
sation cross sections were calculated by Gupta et al. [23]
for 10–2000 eV and Vacher et al [24] for 10-100 eV, while
measured by Vacher et al. [24] for 10–100 eV and Bull and
Harland [25] for the energy range 10–300 eV. Momentum
transfer cross sections were calculated and measured by
Homem et al. [21] for 1–500 eV energy range. Homem
et al. [21] and Pastega et al. [22] predicted a strong reso-
nance at 2.6 eV and 8.0 eV. Vibrational modes in excited
Rydberg states of acetone were studied by Shastri et al.
[26], while theoretical estimation of excitation energies
was done by Shastri et al. [27] and Diau et al. [28]. VUV
electronic spectroscopy of acetone was studied by Nobre
et al. [29] using synchrotron radiation. Literature survey
thus reveals that substantial work is done on acetone but
it is fragmentary in terms of its properties and energies.
Thus in this study we provide electron impact cross
sectional data for acetone over a wide spectrum of energy
from 0.1 eV to 5000 eV. For low energy calculations below
the ionisation threshold, we employ the R-matrix for-
malism and for intermediate to high energy calculations,
i.e. beyond ionisation threshold (9.714 eV) to 5000 eV,
we use the SCOP formalism. Combining both the for-
malisms, we are able to compute the total cross sec-
tional data ranging from 0.1 to 5000 eV for cc-pVTZ
basis set. Apart from this, we report here estimation of
new resonances, excitation cross sections, transport and
rate (elastic, excitation, ionisation, inelastic and total)
coefficients for e-acetone interaction. The article is struc-
tured as follows. In Section 2, we discuss the theo-
retical formalism used in the structural, spectroscopic
and in the electron-molecule scattering calculations.
For the structural and spectroscopic calculations, we
have employed the quantum chemistry packages through
GAMESS and through R-Matrix formulations. For the
scattering data, we employed the R-matrix method and
Spherical Complex Optical Potential (SCOP). For eval-
uating ionisation cross sections, the Complex Scattering
Potential-ionisation contribution (CSP-ic) and Binary
Encounter Bethe (BEB) methods are used. Using the
relevant computed data, the transport and rate coef-
ficients are also studied. Section 3 contains the main
results obtained and we draw relevant conclusions in
Section 4.
2. Theoretical methodology
2.1. Computational methods for structural and
spectroscopic study
Quantum chemical calculations of ground state geom-
etry, vibrational frequencies and excitation energies for
acetone were performed using a general ab initio quan-
tum chemistry package GAMESS (US) [30]. The ground
state geometry and vibrational frequencies were com-
puted using hybrid density functional theory (DFT)
with B3LYP [31], PBE0 [32] and X3LYP [33] with sev-
eral basis sets. The extended split valence basis sets 6-
311G with polarisation and diffuse functions added as
well as correlation consistent basis sets like cc-pVnZ
(n = 2−4) are used in the calculations. Of the diverse
functionals and basis set combinations analysed, the suit-
able agreement with ground state experimental values
is obtained for B3LYP/cc-pVTZ. Vertical excited sin-
glet and triplet state energies were then computed using
PBE0/6-311G+(2d,2p), at the ground state optimised
geometry under the time-dependent DFT (TDDFT) for-
malism [34], which is suitable for appropriate excited
states with Rydberg character. From the overlap of initial
and final state wave functions, the inference of the excited
states as valence, Rydberg or mixed states were evalu-
ated by the range of -diagnostic values [35,36]. The
molecular orbital (MO) energies were estimated using
the self consistent field (SCF) and DFT methods and the
 MOLECULAR PHYSICS 3

MO contour plots were analysed using the MacMolPlt and the correct description of long range interactions for
program [37]. higher partial waves are necessary for convergence. Sum-
mation in Equation (1) represents both resonant and
non-resonant collision processes and their mutual inter-
2.2. Low energy formalism (0.1–20 eV) for the
ference effects. Hence, in the internal region the R-matrix
scattering study
represents the full complexity of the multi-electron col-
Present low energy calculations for electron interaction lision process and hence consumes maximum computa-
with acetone are carried out with the R-matrix method. tional time. Static exchange (SE) is the simplest scattering
The key idea in R-matrix theory is to divide the com- model which uses a single target wave function repre-
pletely involved configuration space, which describes the sented at the Hartree–Fock (HF) level. In this model, the
collision process into two regions. This configuration L2 configurations are given simply by placing the scat-
space is separated into an inner and an outer region, by tering electron in unoccupied target (virtual) orbitals of
a sphere of R-matrix radius  a and collision processes in the appropriate symmetry. The N + 1 configuration for a
each region have different physical significance. We have closed shell target can be written as
a distinct representation of the wave function for inner
(HF)N (cont)1
as well as outer region, where at the common boundaries
these wave functions are connected. (HF)N (virt)1
The R-matrix method and its applications to electron-
where HF denotes a single Hartree–Fock determinant,
molecule collisions employing Quantemol-N package are
virt denotes an unoccupied target orbital, and cont
based on highly sophisticated UK molecular R-matrix
denotes a continuum orbital.
code, which is described in our earlier publications
Static exchange plus polarisation (SEP) builds on the
[38–40] and in other literature [41–46]. Therefore, only
SE model by including L2 configurations which involve
short summary is presented in this section to avoid the
promoting an electron from the HF target wave func-
repetition.
tion to a virtual orbital while also placing the scattering
The electronic charge density of the target plus scat-
electron in a target virtual orbital [52]. The SEP model
tering e− is considered inside the inner region. The
expands the SE configurations for a closed shell target
wave function of inner region is constructed by the
with configurations of the form:
close-coupling method [47] and in this region, electron
exchange and correlation effects between the incident (core)Nc (valence)(Nc −1) (virt)2
electron and the target electrons are important [45].
Here N = Nc + Nv , where Nc is the number of electrons
Within this frame, the inner region wave function is writ-
in doubly occupied orbitals and Nv is the number of elec-
ten for N + 1 electrons (where N is target electrons and 1
trons in ‘valence’ orbitals. The additional configurations
is scattering electron) as [42]
in the SEP model allow the use of short-range target
kN+1 (x1 · · · xN+1 ) polarisation effects in the model. The SEP model remains
 basic, but it is found to provide a good representation of
=A aijk N
i (x1 · · · xN )uij (xN+1 ) low-lying resonances, which are essential for providing a
ij
gateway for dissociative electron recombination and are

+ bik χiN+1 (x1 · · · xN+1 ) (1) also involved in dissociative electron attachment.
i Close-coupling (CC) expansions include the use of
several target states in Equation (1). This model usually
Here, A is the antisymmetric operator. The first summa-
employs a complete active spaces (CAS) description of
tion i represents the wave function of ith target state and
these states, as well as (state-averaged) CASSCF orbitals.
uij is the continuum orbitals to represent the scattering
The N + 1 configuration in a CAS model with M active
electron while aijk and bik are the variational parame-
electrons in the CAS are usually defined as
ters determined computationally by the diagonalisation
of N + 1 (target plus scattering electron) Hamiltonian (core)(N−M) CASM (cont)1
matrix. In the second term, the summation is performed
(core)(N−M) CAS(M+1)
over χi for N + 1 electrons and represents L2 function
with zero amplitude at the R-matrix boundary. The con- (core)(N−M) CASM (virt)1
tinuum orbitals are represented by the orbitals specified
(core)(N−M) CAS(M−1) (virt)2
by Faure et al. [48]. Born closure [49–51] is used for
the inclusion of the higher partial waves for l > 4, as The first and second types of configurations are often
acetone has permanent dipole moment (2.9298 Debye) used, while the third and fourth tend to be needed for
4 D. PRAJAPATI ET AL.

targets with large polarisabilities. The R-matrix approach
necessitates the calculation of energies and wavefunc-
tions for N and N + 1-electron systems. The N-electron
system is commonly referred to as the target and the
N + 1 electron wavefunctions are referred to as the scat-
tering wavefunctions.
2.4.1. Complex scattering potential-ionisation
contribution (CSP-ic)
The electron impact energy-dependent inelastic cross
sections Qinel (Ei ) has two major components, one due to
discrete electronic excitations and the other contribution
due to the ionisation continuum, viz.,

Qinel (Ei ) = Qexc (Ei ) + Qion (Ei ) (3)

2.3. Intermediate to high energy formalism
(ionisation threshold to 5 keV) for scattering study where Qexc (Ei ) is the sum over excitation cross sections
We have employed Spherical Complex Optical Poten- for all permissible electronic transitions that are discrete
tial (SCOP) method to calculate the scattering cross in nature, while Qion (Ei ) takes into account the total
section in intermediate to high energy range for elec- ionisation cross sections induced by an incident elec-
tron–acetone interactions. Our calculated ionisation tron. The first term on the right side arises mainly from
potential through GAMESS for acetone is 9.714 eV. So the low lying dipole transitions, and the contribution
we have calculated scattering cross section from 10 eV of Qexc (Ei ) to inelastic cross sections decreases com-
to 5000 eV using SCOP formalism. Total elastic and total pared to the Qion (Ei ), with increase of incident energy.
inelastic cross sections are added up to obtain the provide By definition,
total cross section as
Qinel (Ei ) ≥ Qion (Ei ) (4)
QT (Ei ) = Qel (Ei ) + Qinel (Ei ) (2)
Equation (4) is an important inequality which is key
where Qel (Ei ) accounts cross sections for elastic chan- point for CSP-ic method. Here, we define R(Ei ) as inci-
nels and Qinel (Ei ) accounts cross sections for inelastic dent energy-dependent ratio of two inelastic part of the
channels. With the use of potential field parameters and cross sections as
partial wave method, Cox and Bohnam had derived elas- Qion (Ei )
tic electron scattering amplitudes for neutral atoms [53]. R(Ei ) = (5)
Qinel (Ei )
Using these potential field parameters, we obtained the
molecular charge density taking into account the struc- such that 0 < R ≤ 1.
tural properties of target [54] and utilised to construct Elaborately, this ratio is redefined in terms of three
the static field, local exchange, polarisation, and absorp- parameters c1 , c2 and a as
tion potentials [55,56]. The sum of these four potentials
 
represent the optical potential. We expand this opti- c2 lnU
cal potential around the centre of mass of the acetone R(Ei ) = 1 − f (U) = 1 − c1 + (6)
U+a U
and considered the spherical term in the expansion.
Using this complex spherical interaction potential, in the where U = EIi , dimensionless variable and parameters
Schrodinger equation by partial wave analysis to yield ’c1 ’, ’c2 ’ and ’a’ are determined by imposing following
various complex phase shifts, which are then used to physical conditions for the ratio R(Ei ), ’I’ denotes the
compute various cross sections [57]. ionisation potential for target molecule.
Details of the SCOP method and its application to
electron-molecule collisions, can be found in our ear- ⎧
⎪
⎨= 0, Ei ≤ I
lier publications [39,40,54,58–61] and in other literature
R(Ei ) = Rp , Ei = Ep (7)
[55,56,62,63]. ⎪
⎩∼
= 1, Ei  Ep

2.4. Ionisation cross sections
For the computation of electron impact ionisation
cross sections, we have employed Complex Scattering
Potential-ionisation contribution (CSP-ic) and Binary
Encounter Bethe (BEB) formalisms starting from
ionisation threshold to 5000 eV, as discussed
below.
Here, Rp is a model parameter corresponds to the value
of the ratio at the peak energy (Ep ) of the inelas-
tic cross section. The three conditions are discussed
in detail in our earlier publications [64,65] and hence
skipped here. Equations (5)– (7) define the present
CSP-ic method and used to extract the ionisation cross
sections.
 MOLECULAR PHYSICS 5

2.4.2. Binary encounter Bethe (BEB) −1

Another type of effective collision frequency ν̄eff is
The Binary Encounter Bethe model incorporates the introduced for correct form of dc conductivity as
Mott cross section with the high-T behaviour of the Bethe
cross section. The theory has no fitting parameters and  5/2 ∞
 2
−1 8 me v3 −m ev
provides for the ionisation cross section per molecular ν̄ = e 2kTe
dv
orbital with a simple analytical formula. The total cross 3π 1/2 N 2kTe 0 Qm (v)
(10)
section of ionisation for a target is obtained by sum-
ming these cross sections of individual molecular orbital
−1
for incident electron energy (E) higher than the bind- The explicit form of ν̄eff is related to the drift velocity
ing energy (B). To compute ionisation cross sections, of electrons in a gas, for the Maxwell distribution. When
we require binding energy B, orbital kinetic energy U, Qm (v) is proportional to ν̄ −1 and two effective collision
electron occupancy number N and a dipole constant Q frequencies < ν > and ν̄ agree.
for each molecular orbital [66,67]. The BEB ionisation The mean free path (λ), Diffusion (D) and Mobility
cross section for electrons in molecular orbital with bind- (μ) coefficients are calculated from the effective collision
ing energy B and orbital kinetic energy U through an frequency by the expressions
incoming electron energy T is
 
8kTe
  λ= ν̄ −1 (11)
S 1 1 π me
σBEB (t) = Q 1 − 2 lnt  
t+u+1 2 t kTe

   D= ν̄ −1 (12)
1 lnt me
+ (2 − Q) 1 − − (8)
t t
and
 
where t = T/B and u = U/B are normalised incident e
and kinetic energies, S = 4πa20 (R/B)2 , a0 = 0.52918 Å, μ= ν̄ −1 (13)
me
R = 13.6057 eV and dipole constant Q = 1.
In Equation (8), the term on the right-hand side rep- respectively, assuming that when the ambient electrons
resents distant collisions which have large impact param- do have a Maxwellian distribution of velocities.
eter and are dominated by the dipole interactions, while Rate Coefficients are obtained by making use of elastic
the other terms on the right-hand side indicate close col- and inelastic cross sections [71], as
lisions which have small impact parameter. The following
 1/2  3/2 ∞
 
logarithmic term introduced from the interference of the 8 1 i − k ETe
direct and exchange scattering described by the Mott Ki = EQ (E)e B dE
me π kB Te 0
cross section [66]. (14)

2.5. Transport and rate coefficients where Qi (E) = 0 up to the threshold. i = 0, 1, 2, 3, 4

The effective electron–molecule collision frequency νeff
in a Maxwellian plasma can be obtained from the
momentum transfer cross sections, Qm (ν) as follows
[68,69]
 5/2
∞
 2
8 me
< ν >= N v5 Qm (v)e
3π 1/2 2kTe 0 The ground state electronic configuration for e −
where me is the mass of electron, Te is the temperature
of electron, k is Boltzmann’s constant, v is the velocity
and N is the number density of the gas particles. < ν >
represents the effective collision frequency for electrical
conductivity of an ac field [69,70].
for the elastic and few excited states respectively. The
rate coefficients for elastic and inelastic processes are
computed upto 10,000◦ K.
3. Results and discussion
−m ev 3.1. Target model
2kTe
dv
(9) ((CH3 )2 CO) in C2v symmetry is 1(a1 )2 , 2(a1 )2 , 1(b2 )2 ,
3(a1 )2 , 4(a1 )2 , 5(a1 )2 , 2(b2 )2 , 6(a1 )2 , 3(b2 )2 , 7(a1 )2 ,
1(b1 )2 , 8(a1 )2 , 1(a2 )2 , 4(b2 )2 , 2(b1 )2 , 5(b2 )2 . For CAS-
CI method, out of 32 electrons of acetone, we have were
frozen 24 electrons in 12 orbitals: 1a1 , 2a1 , 3a1 , 4a1 , 5a1 ,
6a1 , 7a1 , 8a1 , 1b1 , 1b2 , 2b2 , 3b2 and the remaining 8 elec-
trons are allowed to move freely in the active space of
6 D. PRAJAPATI ET AL.
Figure 1. (a) Schematic diagram, (b) 3D total electron density and (c) 3D molecular electrostatic potential of acetone molecule.
8 target occupied molecular orbitals: 1a2 , 4b2 , 2b1 , 5b2 .
9a1 , 10a1 , 6b2 , 3b1 , while for SEP and SE method all
electrons were frozen in the lowest configuration. Four
virtual molecular orbitals (2 of A1 , 1 of B1 , 1 of B2 and
0 of A2 ) of CI method, forty (14 of A1 , 7 of B1 , 13 of B2
and 6 A2 ) of SEP, while three (1 of A1 , 0 of B1 , 2 of B2
and 0 of A2 ) of SE, are allocated for augmentation to the
continuum orbitals and were used for the construction
of the N + 1 trial eigenkets. Acetone in its ground state
belongs to C2v point group with CCCO group in the YZ
plane. Equilibrium ground state geometry with total elec-
tron charge density and molecular electrostatic potential
for acetone molecule is shown in Figure 1.
The assignments for molecular orbitals (MOs) with
their binding energies and contour plots are tabulated
in Table 1. The orbital 5b2 shows the highest occupied
molecular orbital (HOMO) of valence type and is bond-
ing in nature, while orbital 3b1 represents the lowest
occupied molecular orbital of π ∗ in nature. The two MOs
just below the HOMO, 2b1 (HOMO-1) and 4b2 (HOMO-
2) are described as π and σ types respectively which are
in good agreement with the predicted molecular orbitals
by Shastri et al. [27]. The 8a1 (HOMO-3) has been inter-
preted as non-bonding n type which is in good agreement
with Diau et al. [28] while Pasteka et al. [72] consid-
ered this as σ type nature. The 3b1 (LUMO) and 9a1
(LUMO+1) show valence π ∗ type and 3s Rydberg type
in nature. The next few LUMO corresponds to Rydberg
in nature, identified as s, p and d types based on their
energy and symmetry classification under the C2v point
group. Orbital s, pz , dz2 and dx2 −y2 belong to a1 , px and
dxz belong to b1 , py and dyz belong to b2 , while dxy belongs
to a2 [73].
Table 2 contains the target properties for acetone.
R-matrix formalism is employed to calculate the tar-
get properties for CAS-CI, SEP and SE, while hybrid
GGA B3LYP function is used for the DFT calculation
by GAMESS. The self-consistent field (SCF) calculations
yielded the ground state energy of −191.87 Hartree,
−191.58 Hartree and −191.58 Hartree, respectively using
CI, SEP and SE models by Quantemol-N [42], and it
is in accordance with −193.11 Hartree obtained using
B3LYP by GAMESS [30]. Present ionisation potential
calculated by B3LYP is in excellent agreement with the
experimental data of CCCBDB [74]. Present polarisabil-
ity, dipole Moment and rotational constants computed
from CAS-CI, SEP, SE and B3LYP are in good agreement
with the available theoretical results of Pastega et al. [22]
and experimental data of CCCBDB [74].
3.2. Vibrational frequencies and IR spectrum
The IR absorption spectrum of acetone in the gas phase
for the region 0–3500 cm−1 is shown in Figure 2. Table 3
provides the details of observed peaks, their associ-
ated frequency and proposed vibrational assignment pre-
dicted at B3LYP/cc-pVTZ level of theory in comparison
with previous available experiential values of CCCBDB
[74]. The present molecule consists of 10 atoms, hence
undergoes 24 normal modes of vibrations. Of the 24 nor-
mal modes of vibrations, ν1 to ν8 belong to a1 , ν9 to ν12
belong to a2 , ν13 to ν16 belong to b1 and ν17 to ν24 belong
to b2 . In agreement with C2v symmetry, all the compo-
nents of a2 for infrared absorption are inactive. In the
IR spectrum, the most intense peak found at 1792 cm−1 ,
which is due to the CO stretch of v3 . There are two vibra-
tions due to CC stretch, very strong at 1229 cm−1 and
weak at 780 cm−1 in b2 and a1 mode respectively. Peaks
at 1386 cm−1 and 1385 cm−1 show features due to CH3
s-deformation in b2 and a1 while 1471 cm−1 and 1491
cm−1 show features due to deformation of CH3 in b2 and
a1 mode respectively. CO in-plane and out of plane bend-
ing is observed at 531 cm−1 and 486 cm−1 in b2 and b1
mode respectively.
3.3. Vertical electronic excited energies
In Table 4 and 5, we have estimated vertical excited
singlet and triplet energies using TDDFT/PBE0/6-
311G+(2d,2p) and R-matrix/CAS-CI level of theory.
 MOLECULAR PHYSICS 7

Table 1. Molecular orbital (MO) symmetries, binding energies, and contour plots of acetone ((CH3 )2 CO).
MO(Sym.) B.E. (eV) Description Molecular Orbital MO(Sym.) B.E. (eV) Description Molecular Orbital
8a1 (H − 3) -11.01 V (n ) 11a1 (L + 5) 1.83 R (3dx2 −y2 )

4b2 (H − 2) -10.65 V (σ ) 7b2 (L + 6) 2.26 R (3dyz )

2b1 (H − 1) -10.16 V (π ) 2a2 (L + 7) 2.35 R (3dxy )

5b2 (H) -9.71 V (n) 12a1 (L + 8) 2.74 R (3dz2 )

3b1 (L) -0.29 V (π ∗ ) 13a1 (L + 9) 3.07 R (4s)

9a1 (L + 1) 0.39 R (3s) 5b1 (L + 10) 3.09 R (3dxz )

6b2 (L + 2) 1.09 R (3py ) 8b2 (L + 11) 3.52 R (4py )

4b1 (L + 3) 1.44 R (3px ) 9b2 (L + 12) 4.15 R (4dyz )

10a1 (L + 4) 1.56 R (3pz ) 3a2 (L + 13) 5.87 R (4dxy )

For TDDFT, along with excitation energies, initial and
final MOs, transition amplitude, oscillator strengths (f ),
lambda diagnostic ( and) values, assignment and type of
state computed for acetone molecule. Rydberg, valence
or mixed type of the transitions were identified from the
lambda value (0 ≤  ≤ 1) [27], which is a measure of
the overlap between initial and final MOs. In general, a
low lambda value ( < 0.3) indicates a Rydberg state,
an intermediate lambda value (0.3 <  < 0.45) indicates
mixed state, i.e. Rydberg/valence nature, while a high
lambda value ( > 0.45) shows a localised nature of final
wave function associated with a valence state. Nature of
transition is also incorporated with the molecular orbital
shown in Table 1.
The first excitation state 1 A2 , belongs to a transi-
tion from highest occupied MO 5b2 to lowest occu-
pied MO 3b1 is valence in nature, as evident from the
 parameter (0.494). The next few transitions from
5b2 (H) to 9a1 (L + 1), 6b2 (L + 2), 4b1 (L + 3), 10a1 (L +
4), 11a1 (L + 5), 7b2 (L + 6), 2a2 (L + 7), 12a1 (L + 8) are
Rydberg in nature and indicate the transitions from non
bonding n MO to 3s, 3py , 3px , 3pz , 3dx2 −y2 , 3dyz , 3dxy ,
and 3dz2 respectively. Excitation energies estimated from
present TDDFT and R-matrix are also compared with
available experimental data of Shastri et al. [26] and com-
puted results of Shastri et al. [27] and Diau et al. [28],
which is found to be overall in good agreement. The tran-
sition from 4b2 (H − 2) to 3b1 (L), 5b2 (H) to 5b1 (L + 10)
8 D. PRAJAPATI ET AL.

Table 2. Calculated target properties of acetone ((CH3 )2 CO).

Target property (unit) Present
Quantemol-N GAMESS Others
CAS-CI SEP SE DFT/B3LYP Theo. [22] Exp. [74]
Ground State Energy (Hartree) −191.87 −191.58 −191.58 −193.11
Ionisation Potential (eV) – – – 9.7140 9.7030
Polarisability(Å3 ) 6.3380 – – 6.0290 6.096 6.2700
Dipole Moment (debye) 2.9298 2.9299 2.9299 2.8512 3.44 2.8800
Rotational Constants (cm−1 ) A 0.3364 0.3364 0.3364 0.3438 0.3390
B 0.2820 0.2820 0.2820 0.2819 0.2840
C 0.1628 0.1627 0.1627 0.1644 0.1637

Figure 2. Infrared absorption spectrum for acetone.

Table 3. Vibrational symmetry, frequency and IR intensity of acetone ((CH3 )2 CO).
Mode Frequency Red. Mass IR Intensity Exp. [74]
(Sym) Description (cm−1 ) (u) (D2 /uÅ2 ) (cm−1 )
ν1 (a1 ) CH3 d-stretch 3134 1.1012 0.1813 3019
ν2 (a1 ) CH3 s-stretch 3030 1.0372 0.1703 2937
ν3 (a1 ) CO stretch 1792 9.6260 4.1304 1731
ν4 (a1 ) CH3 d-deform 1471 1.0697 0.6460 1435
ν5 (a1 ) CH3 s-deform 1385 1.2224 0.4585 1364
ν6 (a1 ) CH3 rock 1079 1.5734 0.0007 1066
ν7 (a1 ) CC stretch 780 3.6358 0.0441 777
ν8 (a1 ) CCC deform 375 2.1655 0.0332 385
ν9 (a2 ) CH2 d-stretch 3075 1.0983 2963
ν10 (a2 ) CH3 d-deform 1469 1.0511 1426
ν11 (a2 ) CH3 rock 883 1.2113 877
ν12 (a2 ) Torsion 35 1.0175 105
ν13 (b1 ) CH2 d-stretch 3082 1.0987 0.4744 2972
ν14 (b1 ) CH3 d-deform 1491 1.0446 0.4392 1454
ν15 (b1 ) CH3 rock 1118 2.0015 0.0608 1091
ν16 (b1 ) CO op-bend 486 1.9767 0.0093 484
ν17 (b1 ) Torsion 130 1.1231 0.0001 109
ν18 (b2 ) CH3 d-stretch 3133 1.1007 0.2960 3019
ν19 (b2 ) CH3 s-stretch 3023 1.0373 0.0283 2937
ν20 (b2 ) CH3 d-deform 1460 1.0448 0.0280 1410
ν21 (b2 ) CH3 s-deform 1386 1.3927 1.3158 1364
ν22 (b2 ) CCstretch 1229 2.8358 1.7847 1216
ν23 (b2 ) CH3 rock 881 1.5810 0.2316 891
ν24 (b2 ) CO ip-bend 531 3.5586 0.3628 530

and 8a1 (H − 3) to 9a1 (L + 1) indicates n − π ∗ , n − 4py also report that n − 3px , is dipole forbidden transition as
and n − 3s are mixed type in nature as their  param- having zero oscillator strength, hence is not observed in
eter belongs to 0.308, 0.414 and 0.302 respectively. We earlier studies [26,29].
 MOLECULAR PHYSICS 9

Table 4. Calculated singlet excited state energies (in eV) of acetone.

Present Others
Symmetry Initial Final Amp f and Assignment Type TD DFT R-matrix Exp. [26] Theo. [27] Theo.[28]
1 1 A2 5b2 (H) 3b1 (L) 1.02 0.000 0.494 n − π∗ V 4.34 4.43 4.40
1 1 B2 5b2 (H) 9a1 (L + 1) −0.99 0.029 0.220 n − 3s R 6.09 5.78 6.35 6.03 6.17
1 1 A1 5b2 (H) 6b2 (L + 2) −0.99 0.002 0.229 n − 3py R 7.02 7.40 7.00 7.07
2 1 A2 5b2 (H) 4b1 (L + 3) −0.99 0.000 0.198 n − 3px R 7.11 7.36 7.27 7.37
2 1 B2 5b2 (H) 10a1 (L + 4) −0.98 0.028 0.199 n − 3pz R 7.44 7.45 7.45 7.30 7.42
3 1 B2 5b2 (H) 11a1 (L + 5) 0.98 0.015 0.260 n − 3dx2 −y2 R 7.64 8.09 7.63 7.71
2 1 A1 5b2 (H) 7b2 (L + 6) −0.99 0.056 0.203 n − 3dyz R 7.91 7.92 7.71 7.96 8.08
1 1 B1 5b2 (H) 2a2 (L + 7) −1.00 0.016 0.119 n − 3dxy R 8.12 8.10 8.16 8.20 8.33
4 1 B2 5b2 (H) 12a1 (L + 8) 0.99 0.003 0.222 n − 3dz2 R 8.43 8.32 8.54
3 1 A2 4b2 (H − 2) 3b1 (L) 0.99 0.000 0.308 σ − π∗ R-V 8.54 8.38 8.36
2 1 B1 8a1 (H − 3) 3b1 (L) −0.99 0.001 0.515 n − π ∗ V 8.64 8.74 8.67
4 1 A2 5b2 (H) 13a1 (L + 9) −0.99 0.000 0.177 n − 4s R 8.76 8.21 8.69
5 1 B2 5b2 (H) 5b1 (L + 10) 0.99 0.016 0.280 n − 3dxz R 8.98 8.76 8.87
3 1 B1 2b1 (H − 1) 9a1 (L + 1) −0.99 0.005 0.246 π − 3s R 9.10 8.47 8.79 8.88
3 1 A1 5b2 (H) 8b2 (L + 11) 0.76 0.149 0.414 n − 4py R-V 9.26 8.56 9.27
4 1 A1 2b1 (H − 1) 3b1 (L) −0.77 0.097 0.524 π − π∗ V 9.35 9.35 8.82 8.84
6 1 B2 4b2 (H − 2) 9a1 (L + 1) 0.99 0.032 0.276 σ − 3s R 9.53 9.49
4 1 B1 5b2 (H) 3a2 (L + 13) −0.99 0.002 0.192 n − 4dxy R 9.63
7 1 B2 5b2 (H) 9b2 (L + 12) −0.99 0.040 0.258 n − 4dyz R 9.66 9.76
5 1 A1 8a1 (H − 3) 9a1 (L + 1) −0.96 0.121 0.302 n − 3s R-V 9.87
5 1 A2 2b1 (H − 1) 6b2 (L + 2) −0.99 0.000 0.170 π − 3py R 9.99 9.68 9.71
f : Oscillator Strength; ∧ : Lambda Diagnostic; Amp : TDDFT excitation amplitude;
∗ H : HOMO; L : LUMO; V : Valence; R : Rydberg

Table 5. Calculated triplet excited state energies (in eV) of acetone.

Present Others
Symmetry Initial Final Amp and Assignment Type TDDFT R-matrix Theo. [27] Theo. [72]
13 A2 5b2 (H) 3b1 (L) −0.937 0.491 n − π∗ V 3.66 3.80 4.09
13 A1 2b1 (H − 1) 3b1 (L) 0.807 0.803 π − π∗ V 5.46 5.66 6.22
13 B2 5b2 (H) 9a1 (L + 1) −0.981 0.220 n − 3s R 6.02 5.72 5.96 6.51
2 3 A1 5b2 (H) 6b2 (L + 2) −0.984 0.225 n − 3py R 6.89 6.88 7.50
23 A2 5b2 (H) 4b1 (L + 3) 0.979 0.200 n − 3px R 7.08 7.24 7.50
23 B2 5b2 (H) 10a1 (L + 4) 0.964 0.200 n − 3pz R 7.36 7.25 7.51
33 B2 5b2 (H) 11a1 (L + 5) −0.958 0.260 n − 3dx2 −y2 R 7.55 7.55
13 B1 8a1 (H − 3) 3b1 (L) −0.872 0.507 n − π ∗ V 7.73 7.93 8.60
33 A1 5b2 (H) 7b2 (L + 6) 0.980 0.203 n − 3dyz R 7.84 7.62 7.91
23 B1 5b2 (H) 2a2 (L + 7) −0.993 0.119 n − 3dxy R 8.09 8.19
33 A2 4b2 (H − 2) 3b1 (L) 0.940 0.317 σ − π∗ R-V 8.30 8.13 8.96
43 B2 5b2 (H) 12a1 (L + 8) −0.980 0.224 n − 3dz2 R 8.37 7.98 8.28
43 A2 5b2 (H) 5b1 (L + 9) 0.976 0.180 n − 3dxz R 8.74 8.98 8.75
53 B2 5b2 (H) 13a1 (L + 10) −0.968 0.281 n − 4s R 8.82 8.57
33 B1 2b1 (H − 1) 9a1 (L + 1) 0.972 0.247 π − 3s R 9.00 8.66 9.62
4 3 A1 5b2 (H) 8b2 (L + 11) 0.972 0.233 n − 4py R 9.21 9.12
63 B2 4b2 (H − 2) 9a1 (L + 1) 0.956 0.276 σ − 3s R 9.35 9.30
73 B2 5b2 (H) 14a1 (L + 12) 0.974 0.260 n − 4pz R 9.55
43 B1 5b2 (H) 3a2 (L + 13) −0.985 0.195 n − 4dxy R 9.59
53 A1 8a1 (H − 3) 9a1 (L + 1) 0.886 0.300 n − 3s R-V 9.64
53 B1 7a1 (H − 5) 3b1 (L) −0.853 0.492 n − π ∗ V 9.89
f : Oscillator Strength; ∧ : Lambda Diagnostic; Amp : TDDFT excitation amplitude;
∗ H : HOMO; L : LUMO; V : Valence; R : Rydberg

Present triplet vertical excitation energies are esti-
mated and compared with the calculated results of Shas-
tri et al. [27] and Pasteka et al. [72] in Table 5. First
two triplet excitations from 5b2 (H) and 2b1 (H − 1) to
3b1 (L) indicate n − π ∗ and π − π ∗ transitions, which
are valence type in nature. Next few transitions from
n to 3p and 3d orbitals are of n−3s, n − 3py , n − 3px ,
3dn−x2 −y2 , n − 3dyz ,n − 3dxy , n − 3dz2 and n − 3dxz ,
which belongs to Rydberg type due to their  diagnostics.
All the excitation energies fairly agree with the values
available in literature [27,72].
3.4. Eigenphase sum
Figure 3 shows eigenphase sum for e-acetone in C2v point
group symmetry, which provides an important diagnos-
tic of scattering calculation. Here we present eigenphase
curve for symmetry states a1 , b1 , b2 and a1 from the sum
10 D. PRAJAPATI ET AL.

Figure 3. Eigenphase sum for e-acetone, where the solid line represents 2 A1 symmetry state, dash line represents 2 B1 state, dot line
represents 2 B2 state and dash dot line represents the 2 A2 state of C2v point group.

of eigenvalues of K-matrix for CAS-CI model. These Table 6. Resonance (Er ) and width parameter (r ) of acetone
were further analysed to obtain the position and width of ((CH3 )2 CO) using R-matrix.
resonances by performing Breit–Wigner fits to the eigen- Present Others
phase diagram through the program module RESON Symmetry Model Description Er (eV) r (eV) Er (eV)
[44]. Table 6 indicates total 20 resonances corresponding 2A
1 CAS-CI EEFR ( n – σ ∗ ) 5.84 0.155
to 2 A1 , 2 B1 , 2 B2 , and 2 A2 , which can be further classi- SEP EEFR ( n – δ ∗ ) 7.63 0.020
SEP EEFR ( n – σ ∗ ) 8.26 0.110 8.0 [22]
fied as Electronic Excited Feshbach Resonance (EEFR) SEP EEFR ( n – σ ∗ ) 8.87 0.030
and Shape Resonance (SR). Tables 4 and 5 provide the SEP EEFR ( π – σ ∗ ) 9.22 0.050
transition details for resonance and width parameter. For SEP EEFR ( σ – σ ∗ ) 9.51 0.040 10.0 [21]
2 A symmetry, we have predicted one δ ∗ EEFR at 7.63 eV
2B
1 CAS-CI SR ( π ∗ ) 0.50 0.200
1 SEP SR ( π ∗ ) 2.56 0.012
with the width of 0.020 eV and four σ ∗ EEFR at 5.84 eV, SEP EEFR ( π – π ∗ ) 5.66 0.047
SEP EEFR ( π – π ∗ ) 9.33 0.056 8.0 [21]
8.26 eV, 8.87 eV, 9.22 eV and 9.51 eV of width 0.155 eV, SEP EEFR ( n’ – π ∗ ) 9.83 0.070
0.110 eV, 0.030 eV, 0.050 eV and 0.040 eV respectively. 2B
2 SEP SR ( π ∗ ) 2.86 0.075 2.6 [21,22]
SR ( π ∗ )
Pastega et al. [22] and Homem et al. [21] found σ ∗ res- CAS-CI
SEP EEFR ( n – π ∗ )
3.86
7.31
0.103
0.001
onance around 8.0 and 10.0 respectively. For 2 B1 sym- SEP EEFR ( n – π ∗ ) 8.25 0.006
metry, we found the π ∗ low lying resonance at 0.50 eV, SEP EEFR ( n – π ∗ ) 9.41 0.030
2A CAS-CI EEFR ( n – δ ∗ ) 5.66 0.246
π ∗ shape resonance at 2.56 eV and three EEFR at 5.66 eV,
2
SEP EEFR ( n – δ ∗ ) 5.70 3.870
9.33 eV and 9.83 eV in comparison with 8.0 eV resonance SEP SR ( δ ∗ ) 6.28 0.540
CAS-CI SR ( δ ∗ ) 8.21 0.910 8.0 [21]
of Homem et al. [21]. Present study confirmed the find-
EEFR: Electronic Excited Feshbach Resonance; SR: Shape Resonance.
ing of Homem et al. [21] and Pastega et al. [22] that a
feature of e-acetone scattering is the existence of a π ∗ 15 eV and 20 eV, calculated in SE, SEP and CAS-CI
shape resonance at 2.6 eV for 2 B2 symmetry component. model and compared with experimental measurements
As 2 A2 symmetry component belongs to δ ∗ resonances, of Pastega et al. [22] and theoretical data of Homem et al.
we found two EEFR at 5.66 eV and 5.70 eV and two SR at [21] and Pastega et al. [22]. The present study employed
6.28 eV and 8.21 eV in comparison with 8.0 eV resonance Born correction method [76] on the scattering ampli-
from Homem et al. [21]. tude to compute DCS, while for CAS-CI method we
have also employed without Born correction method.
Present SE, SEP and CAS-CI with Born correction are in
3.5. Differential cross sections
excellent agreement, while the data of CAS-CI without
We have employed POLYDCS suite of Sanna and Born correction underestimate at high angle as expected.
Gianturco [75] to calculate differential cross sections. At low angle due to the large dipole moment, differ-
Figures 4 and 5 show differential cross sections for inci- ential cross sections are dominated by strong peaks in
dent scattering energies 1 eV, 3 eV, 5 eV, 7 eV, 10 eV, 12 eV forward scattering direction. Our DCSs are qualitatively

Figure 4. Differential Cross Sections (DCS) for incident energy of
1 eV, 3 eV, 5 eV and 7 eV, where the solid line represents calculated
present CAS-CI with Born correction, dash line represents calcu-
lated present CAS-CI without Born correction, short dash line rep-
resents calculated present SEP with Born correction, dot line rep-
resents calculated present SE with Born correction, dash dot line
represent calculated data by Homem [21] using MCOP method,
dash dot and dash double dot line represent calculated and solid
sphere represents experimental measured data by Pastega [22]
using SMC-SEP, IAM-SCAR and HREELS respectively.
Figure 5. Differential Cross Sections (DCS) for incident energy
of 10 eV, 12 eV, 15 eV and 20 eV, where the solid line represents
calculated present CAS-CI with Born correction, dash line repre-
sents calculated present CAS-CI without Born correction, short
dash line represents calculated present SEP with Born correction,
dot line represents calculated present SE with Born correction,
dash dot line represent calculated data by Homem [21] using
MCOP method, dash dot and dash double dot line represent calcu-
lated and solid sphere represents experimental measured data by
Pastega [22] using SMC-SEP, IAM-SCAR and HREELS respectively.
in very good general agreement with previous exper-
imental and theoretical results [21,22]. Present DCS
between 7 and 10 eV show a weak double-dip structure,
which indicate the d-wave resonances. Figure 6 shows the
three-dimensional rotationally summed elastic differen-
tial cross section from 0.1 to 20 eV range.
MOLECULAR PHYSICS 11
3.6. Momentum transfer cross sections
Momentum transfer cross sections are very sensitive to
correlation effects for backward scattering, we present
our MTCS data using R-matrix for e-acetone in the low
energy regime. MTCS, for electron distribution function,
is further used as an input for Boltzman equation. From
Figure 7, we have provided the MTCS for the energy
range 1 – 20 eV in comparison with the theoretical data
of Homem et al. [21]. The MTCS curve of Homemm et al.
shows a π ∗ resonance at 2.6 eV. The sharp increase at low
energies is an effect due to the permanent electric dipole
moment of the acetone.
3.7. Elastic cross sections
Symmetry decomposition of C2v point group for electron
impact elastic cross sections for energy range 0–20 eV
are reported in Figure 8. Present symmetry elastic cross
sections are decomposed to A1 , B1 , B2 and A2 using CAS-
CI and SEP methods and compared with the theoretical
results of Pastega et al. [22] and Homem et al. [21]. The
dip minima from present CAS-CI of 2 B1 at 0.5 eV is a val-
idation of low lying resonance at 0.50 eV of width 0.2 eV
and structure from SEP at 2.56 eV is a validation of shape
resonance at 2.56 eV of width 0.012. Resonance of dou-
blet B2 at 2.86 eV, 3.86 eV, 7.31 eV, 8.25 eV and 9.41 eV
can be cross verified from the elastic cross sections form
B2 curve obtained by SEP model. Most of the resonances
of Table 6 can be verified from the SEP structures seen in
Figure 8.
In Figure 9, we present elastic cross sections using
CAS-CI, SEP and SE model using the R-matrix for the
energy range 0-17 eV, while from 17 eV to 5000 eV elastic
cross sections are computed using the SCOP formalism.
Pastega et al. [22] have estimated elastic cross sections
using the independent-atom method with screening-
corrected additivity rule (IAM-SCAR) for the energy
range 1–1000 eV and Homem et al. [21] have calculated
elastic cross sections by the molecular complex opti-
cal potential (MCOP) from 1–500 eV and measured for
30–800 eV energy range. Our elastic cross section results
are on higher side due to inclusion of dipole contribu-
tion at low energy. From 40–800 eV experimental values
of Homem et al. are in excellent agreement with present
elastic cross sections data.
3.8. Electronic excitation cross sections
Figure 10 shows the electronic excitation cross section
for e-acetone interaction using the R-matrix method for
low energy region from 0.1 to 20 eV. Electron impact
electronic excitation cross sections for acetone does not
12 D. PRAJAPATI ET AL.
Figure 6. Differential Cross Sections (DCS) for incident energy 0.1 to 20 eV.
Figure 7. Momentum Transfer Cross Sections (MTCS), where the
solid line represents the present calculated data and short dash
line represents calculated results using MCOP method by Homem
[21].
appear to be reported earlier to the best of our knowledge.
Figure 10 gives electron impact excitation cross sections
to the first eight states of acetone using CAS-CI R-matrix
method. The first triplet excitation cross sections belong
to 3 A2 and singlet electronic excited cross sections belong
to 1 A2 , which are highest dominated in comparison with
other electronic excited cross sections, show maximal
excitation cross section at 0.66 and 1.20 eV and sharp fea-
ture at 5.72 and 5.78 eV for the n−3s transition, which
also support the resonance feature for 5.66 and 5.70 eV
from Table 6. For singlet and triplet B2 states, peaks can
be seen at 5.90 and 5.87 eV with a peak value of 0.212
and 0.138 Å2 respectively. The sharp peak at 7.45 eV and
7.98 eV is attributed due to n − 3pz and n − 3pz2 transi-
tions (cf Table 4,5), are supported by the resonance for
2 B between 7 eV and 9 eV.
2
3.9. Ionisation cross sections
In Figure 11, we present the partial ionisation cross sec-
tions using the molecular wave function data which are
computed from the molecular structure code GAMESS
[30]. We present the values of binding energy (B), kinetic
energy (U) and occupation number ( N) for all occupied
MOs of acetone molecule in Table 7. For closed-shell ace-
tone molecule, we used the restricted Hatree–Fork (RHF)
method with a cc-pVTZ basis set using GAMESS. Using
the input parameters of Table 7 for BEB formalism, we
present the ionisation cross sections for each electron
occupied molecular orbital 1a1 , 2a1 , 1b2 , 3a1 , 4a1 , 5a1 ,
2b2 , 6a1 , 3b2 , 7a1 , 1b1 , 8a1 , 1a2 , 4b2 , 2b1 and 5b2 for
acetone molecule from ionisation threshold to 5000 eV.
By summing up these partial ionisation cross sections,
we found the total ionisation cross sections for acetone.
From Figure 11, we can estimate that the contribution
from the ground state 1a1 is minimum, and it is increas-
ing with the electron occupation in orbitals and found
maximum for highest occupied MO 5b2 , as it has more
tendency to be ionised.
 MOLECULAR PHYSICS 13

Figure 8. Symmetry decomposition of the integral cross section for e-acetone obtained in C2v point group, where the solid line repre-
sents the calculated present CAS-CI, dot line represents the calculated present SEP, short dash line represents the present SE dash line
represents the calculated data by Pastega [22] and dot line represents calculated data by the Homem [21].

Table 7. Orbital input parameters for acetone.

MO B.E. (eV) K.E.(eV) N)
1a1 558.98 794.80 2
2a1 308.33 436.22 2
1b2 305.69 435.90 2
3a1 305.69 435.93 2
4a1 37.71 71.88 2
5a1 28.30 39.22 2
2b2 26.31 35.57 2
6a1 20.16 49.43 2
3b2 17.55 37.92 2
7a1 17.31 44.35 2
1b1 16.93 27.08 2
8a1 15.29 37.68 2
1a2 11.01 27.13 2
4b2 10.65 32.43 2
2b1 10.16 46.55 2
5b2 9.71 58.07 2
Figure 9. Elastic cross section for e-acetone, where the dash dou-
ble dot line represents the calculated present CAS-CI, short dot
line represents the calculated present SEP, short dash line repre-
sents the calculated present SE, solid line represents the calcu- Present CSP-ic ionisation cross sections is in good agree-
lated present SCOP, short dash dot line represents calculated data ment with available results of Gupta et al. [23], but slightly
by Pastega et al. [22] using IAM-SCAR, dash line represents calcu- higher at peak values in comparison to present BEB. Ion-
lated data using MCOP and solid sphere represents measured data isation cross section calculated using BEB is in excellent
by Homem et al. [21]. agreement with both experimental and theoretical data of
Vacher et al. [24]. Results of Bull and Harland is in agree-
ment with BEB up to 60 eV and from 60 eV onwards it
Figure 12 indicates the ionisation cross sections for e- slightly overestimates by about 1 Å2 .
acetone using CSP-ic and Binary Encounter Bethe (BEB)
model. The present study provides ionisation cross sec-
3.10. Inelastic cross sections
tions starting from ionisation potential to 5000 eV in and
compared with that estimated ionisation cross sections In Figure 13, we report all the calculated inelastic data
by Gupta et al. [23] up to 2000 eV and by Vacher et al. using R-matrix and SCOP formalism [77]. For low energy
[24] up to 100 eV, while Bull and Harland [25] measured (0.5 –20 eV) we have calculated inelastic cross sections
up to 300 eV and by Vacher et al. [24] up to 100 eV. and total electronic excitation cross sections, while for
14 D. PRAJAPATI ET AL.

Figure 10. Electronic excitation cross sections, where the solid line represents the 3 A2 , dash line represents 1 A2 , dot line represents 3 B2 ,
dash dot line represents 1 B2 , dash dot dot line represents 1 A1 , short dash line represents 3 A1 , shot dot line represents 1 A1 and short dash
dot line represents 3 B2 .

higher energies ( 10–5000 eV), electronic excitation, ion-

isation and total inelastic cross sections are calculated
using SCOP formalism. There is a matching of total
inelastic and excitation cross section by the two differ-
ent formalism at around at 13 and at 17 eV respectively.
Gupta et al. [23] had calculated inelastic cross sections
from 10 to 2000 eV, which is in good agreement with the
present inelastic cross sections. Present total excitation
cross sections of e-acetone scattering are reported for the
wide impact energy (0.5 –5000 eV) for the first time to
the best of our knowledge.

3.11. Total scattering cross sections

Despite the multitude importance of acetone, relatively
few measurements of total cross sections (TCS’s) are
reported in the literature. In Figure 14, we present the
calculated CAS-CI, SEP and SE results using R-matrix
for energy range 0.1–17 eV, while from energy range
17–5000 eV computed TCS using SCOP and are com-
pared with experimental results of Szmytkowski [19] and
Kimura et al. [20] and theoretical results of Homem [21]
and Pastega [22]. Szmytkowski [19] measured TCS’s at
electron-impact energy extending from 0.7 to 400 eV,
using a linear electron-transmission technique, while
Kimura et al. [20] have measured from 1 to 700 eV.
Pastega et al. [22] computed TCS’s from 2 to 1000 eV
from IAM-SCAR calculations while Homem et al. [21]
have calculated in the 1–500 eV range using the MCOP
formalism. Present data provide the TCS’s for the entire
range 0.1 to 5000 eV. Present low energy CAS-CI, SEP,
SE and high energy SCOP results for TCS’s are in
Figure 11. Partial ionisation cross sections, where solid line
(black) represents total ionisation cross sections, 2a1 : solid (royal)
1b2 : short dash dot (red) 3a1 : short dot (blue) 4a1 : short dash
(magenta) 5a1 : dash double dot (olive) 2b2 : dash dot (navy) 6a1 :
dot (violet) 3b2 : dash (purple) 7a1 : solid (wine) 1b1 : short dash
dot (dark yellow) 8a1 : short dot (gray) 1a2 : short dash (green) 4b2 :
dash double dot (orange) 2b1 : dash dot (pink) 5b2 : dot (dark cyan).
excellent agreement with the theoretical results of Pastega
et al. [22] using IAM-SCAR method in the energy range
2–1000 eV.
3.12. Transport and rate coefficients
The numerical values of effective collision frequency
< ν > and ν̄ are computed using present MTCS data.
The effective collision frequency ν̄ can be further used to
 MOLECULAR PHYSICS 15

Table 8. Total Cross Section (TCS) for electron scattering on ace-

tone (Energy Ei is in eV and TCS is in Å2 ). The overall uncertainty of
TCS is ±5% at 0.1-17 eV and 10% at higher energy.
Ei TCS (R-matrix) Ei TCS (SCOP)
0.1 4108.29 17 64.46
0.2 2262.26 18 63.94
0.3 1607.77 20 62.20
0.4 1278.16 30 51.72
0.5 1030.13 40 43.13
0.6 827.71 50 37.34
0.7 722.41 60 33.60
0.8 644.13 80 30.20
0.9 582.38 100 27.86
1 532.17 120 25.85
2 296.31 140 24.08
3 212.18 160 22.53
4 169.59 180 21.15
5 145.00 200 19.93
6 129.21 300 15.40
7 118.08 400 12.51
Figure 12. Ionisation cross sections, where solid line represents 8 109.01 500 10.53
calculated present CSP-ic, dash line represents calculated present 9 101.00 1000 5.82
BEB, dash dot line represents calculated and open circle represents 10 94.31 1500 3.95
11 89.09 2000 2.91
measured data by Vacher et al. [24] and open square represents 12 84.45 2500 2.23
measured data by Bull and Harland [25]. 13 80.11 3000 1.76
14 76.47 3500 1.41
15 72.84 4000 1.15
16 69.00 4500 0.94
17 65.18 5000 0.78

Figure 13. Inelastic cross sections for e-acetone, where the solid
line represents the calculated present Inelastic cross sections
using CAS-CI, dot line represents the calculated present Excita-
tion cross sections using CAS-CI, short dash line represents the
calculated present Inelastic cross sections using SCOP, dash line
Figure 14. Total Scattering Cross Sections (TCS) for electron scat-
represents the calculated present Ionisation cross sections using
tering from acetone, where the present dash double dot line
CSP-ic, dash double dot line represents the calculated present Ion-
represents present CAS-CI without Born Correction, dash line
isation cross sections using BEB, short dash dot line represents the
represents CAS-CI, short dash dot line represents SEP, dot line
calculated present Excitation cross sections using CSP-ic and dash
represents SE, solid line represents SCOP, short dot line repre-
dot line represents the calculated Inelastic cross sections data by
sents MCOP Homem[21], short dash dot line represents IAM-SCAR
Gupta et al. [23].
Pastega [22], circle represents Szmytkowski [19] and square repre-
sents Kimura [20].

estimate the transport coefficients such as mean free path,

diffusion and mobility of electron as shown in Figure 15
using expressions 11, 12 and 13 for a Maxwellian noble-
gas plasma. We have computed transport coefficients for
the temperature range 500 ◦ K to 50000 ◦ K. There are no
results available in the literature to compare the present
transport properties.
For the modelling of heating rates, cross-sections
for processes in which solar photons or photoelectrons
interact with neutral species, and rate coefficients and
product yields for chemical reactions of ions and neu-
tral atmospheric species are required [78]. In Figure 16,
we have shown the temperature depended elastic and
16 D. PRAJAPATI ET AL.
Figure 15. e temperature dependent transport coefficients for acetone.
Figure 16. Rate coefficients, where the solid (black) line repre-
sents total rate coefficients, Elastic CAS-CI: dash (red), Elastic SEP:
short dash dot (blue), Elastic SE: short dot (wine); Excitation rate
coefficients: solid (gray), 3 A2 : short dash dot (dark cyan), 1 A2 : dash
(red), 3 B2 : dot (blue), 1 B2 : dash dot (magenta), 1 A1 : dash dou-
ble dot (olive), 3 A1 : short dash (navy), 1 A1 : shot dot (violet), 3 B2 :
short dash dot (purple); Ionisation: dash double dot (dark yellow);
Inelastic: short dash (orange).
inelastic rate coefficients of acetone for the tempera-
ture range 100 – 100,000 ◦ K. Elastic rate coefficients
have been computed for CAS-CI, SEP and SE mod-
els. Rate coefficient for elastic CAS-CI overestimate the
SEP and SE models. Excitation rate coefficients for first
excited states of CAS-CI i.e. 3 A2 , 1 A2 , 3 B2 , 1 B2 , 1 A1 , 3 A1 ,
1 A and 3 B are predicated. Ionisation rate coefficients
1 2
are computed for CAS-CI model, and summing up the
excitation and ionisation cross sections we deduce the
inelastic rate coefficients. Finally, the elastic and inelastic
rate coefficients are utilised to describe the total rate
coefficients.
4. Conclusion
In summary, the present theoretical study describes an
exhaustive study for the electron impact on acetone
over a wide energy range. More precisely, Eighenpahse
sum, DCS, MTCS, symmetry decomposed cross sections
for C2v point group for elastic electron impact scatter-
ing were studied using R-matrix at low to intermediate
energy regime. Inelastic and excitation cross sections
are studied for the first time. Ionisation cross sections
were computed using CSP-ic and BEB formalism. Elas-
tic, Inelastic and total scattering cross sections for e-
acetone were computed using the amalgamation of two
theoretical formalism i.e. R-matrix for low (0.1 eV) to
intermediate energy while SCOP for intermediate to high
energy (5000 eV). Present calculated results are in good
agreement with available theoretical and experimental
data.
The present study confirms π ∗ shape resonance at
2.86 eV for 2 B2 and σ ∗ resonance around 8 eV for 2 A1
and 2 A2 , in comparison with previous studies [21,22].
Apart from this, low lying π ∗ resonance at 0.50 eV for
2 B , π ∗ shape resonance at 2.56 eV for 2 B and at 3.86 eV
1 1
for 2 B1 , π ∗ electronic excited Feshbach resonances for
2 A at 5.84 eV, 8.87 eV, 9.22 eV, and 9.51 eV; for 2 B at
1 1

5.66 eV, 9.33 eV and 9.83 eV; for 2 B2 at 7.31 eV, 8.25 eV
and 9.41 eV, δ ∗ electronic excited Feshbach resonances
for 2 A1 at 7.63 eV and for 2 B2 at 5.66 eV and 5.70 eV are
reported for the first time. Present resonances are vali-
dated from transitions found in vertical excitation ener-
gies and various structures found in elastic and inelastic
cross sections at respective energies.
The IR spectrum of the acetone molecule in the
0–3500 cm−1 region is reinvestigated and reassigned with
the help of DFT calculations of the ground state structure
and vibrational frequencies. Vertical excitation energy
estimated using TDDFT for singlet and triplet states are
in good agreement with the available value from pre-
vious studies. Transport coefficients such as mean free
path, diffusion, mobility and temperature depended elas-
tic, excitation and ionisation rate coefficients are also
estimated for the first time. The extensive scattering data
reported here for e-acetone will fill the existing void in
the database for this molecule.
Acknowledgments
Minaxi Vinodkumar acknowledges financial support by Sci-
ence and Engineering Research Board (SERB), New Delhi,
through Grant No. EMR/2016/000470.
Author Contributions
Dineshkumar Prajapati: Conceptualisation, data cura-
tion, writing-original draft; Chetan Limbachiya: formal
analysis, writing review; P.C. Vinodkumar: Supervision,
writing-review & editing, project administration; Minaxi
Vinodkumar: funding acquisition, writing-review &
editing.
Disclosure statement
No potential conflict of interest was reported by the author(s).
Funding
This work was supported by Science and Engineering Research
Board [EMR/2016/000470].
ORCID
D. Prajapati http://orcid.org/0000-0002-9374-0029
P. C. Vinodkumar http://orcid.org/0000-0003-2270-7691
C. Limbachiya http://orcid.org/0000-0003-2845-1244
M. Vinodkumar http://orcid.org/0000-0002-1227-4717
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