Journal of Molecular Structure 1299 (2024) 137064

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

Linear and nonlinear optical absorption of 2D monolayer NbOCl2

Na Zhang a, 1, Ning Li b, 1, Li Wang a, Mengtao Sun b, *, Jingang Wang a, *
a
College of Science, Liaoning Petrochemical University, Fushun 113001, China
b
School of Mathematics and Physics, University of Science and Technology Beijing, Beijing 100083, China

A R T I C L E I N F O A B S T R A C T

Keywords: The in-layer crystal structure of a two-dimensional material is stable, but the interaction force between the
Linear optical absorption atomic layers is much weaker. Niobium oxide dichloride (NbOCl2) not only has high second-order nonlinear
Nonlinear optical absorption coefficients unique to common monolayer two-dimensional materials but also weak electronic coupling between
TPA
layers. These characteristics make NbOCl2 very suitable as a quantum light source in quantum optical systems.
TDMD
NbOCl2
This article mainly studies the linear and nonlinear optical absorption of two-dimensional monolayer NbOCl2.
The characterization means include a surface distance projection map and three views, total density of states,
photoelectron spectrum, charge density difference, transition dipole moment density, one-photon absorption
spectrum, and two-photon absorption spectrum. There is a size effect on the total density of states, photoelec­
tronic energy spectrum, and one-photon absorption spectrum, that is, as the size increases, the total density of
states is red-shift, the photoelectronic energy spectrum is blue-shift, and the absorption spectrum has a signifi­
cant red-shift. The charge density difference indicates that there is charge transfer around the Nb atom of
NbOCl2. The transition dipole moment density changes periodically. The study of the two-photon absorption
spectrum shows that it is dominated by a one-step transition. In summary, our work provides an in-depth un­
derstanding of its optical properties and is of great significance for the miniaturization of quantum light sources.

1. Introduction thickness while maintaining the stability of its physical properties, so

As an indispensable part of quantum optical systems, quantum light
sources have always been the focus of research on their miniaturization
[1]. The 2D layered materials, with unique van der Waals structure,
enable bond-free integration without lattice and processing limitations
[2]. They also show enhanced many-body electronic effects and relaxed
phase-matching conditions, leading to large optical nonlinearity at the
2D limit [3], and have therefore attracted intense interest for integrated
nonlinear optical (NLO) optoelectronics and photonics[2,4].
2d materials have defects in the layer, and the physical properties,
especially the optical properties, are very sensitive to the defect density.
Experimental studies of Pepe et al. [5] and Unlu et al. [6] show that one
photon absorption and two photon absorption and multiphoton ab­
sorption can be observed according to defect density and distribution
and laser wavelength. As well as, the in-layer crystal structure of a
two-dimensional material is stable, but the interaction force between the
atomic layers is much weaker [7]. Based on this characteristic, a
monolayer two-dimensional material can maintain the atomic-scale
that the two-dimensional material can be stably and flexibly directly
coupled with various micro-nano-scale optical devices, so it is widely
used in various important components of integrated photonic chips [8].
Although common two-dimensional materials (WS2, WSe2, etc.) have a
large second-order nonlinear coefficient, the thickness of the monolayer
is too thin (<1 nm), resulting in the overall nonlinear signal strength
being very low [9,10]. Interlayer electronic coupling in two-dimensional
materials enables tunable and emergent properties by stacking engi­
neering. However, it also results in significant evolution of electronic
structures and attenuation of excitonic effects in two-dimensional
semiconductors as exemplified by quickly degrading excitonic photo­
luminescence and optical nonlinearities in transition metal dichalcoge­
nides when monolayers are stacked into van der Waals structures. This is
due to the spatial symmetry caused by multilayer stacking, which
weakens or even disappears the second-order nonlinear process [11,12].
Therefore, Gao et al. [13] adopted a new type of van der Waals
crystal, NbOCl2, which not only has high second-order nonlinear co­
efficients unique to common monolayer two-dimensional materials but

* Corresponding authors.
E-mail addresses: mengtaosun@ustb.edu.cn (M. Sun), jingang_wang@lnpu.edu.cn (J. Wang).
1
Equal contribution.

https://doi.org/10.1016/j.molstruc.2023.137064
Received 30 August 2023; Received in revised form 8 November 2023; Accepted 11 November 2023
Available online 21 November 2023
0022-2860/© 2023 Elsevier B.V. All rights reserved.
N. Zhang et al. Journal of Molecular Structure 1299 (2024) 137064

also has weak electronic coupling between layers and asymmetric The TPA cross-section can be defined as:
spatial structure. This characteristic makes its second-order nonlinear
4π 2 a20 α ω2 g(ω)
signal strength increase with the increase of the number of layers of the σ tp = δtp (3)
15c Γf
two-dimensional material, along with a scalable second-harmonic gen­
eration intensity of up to three orders higher than that in monolayer
where a0 , α, c is the Bohr radius, the fine structure constant, and the light
WS2. The two-dimensional van der Waals ferroelectric NbOCl2 was
speed, respectively. g(ω) is the spectral line profile, which is assumed to
found to exhibit an abnormally large anisotropic SHG [14]. Very
be a δ function here, and Γf is level broadening of the final state. δtp is the
recently, the layered ferroelectric (FE) material niobium oxide dihalides
orientational averaging value of the TPA probability[29].
NbOX2 has attracted plenty of interest due to their large, anisotropic
The transition probability δtp can be stated as
[15], and even layer-independent SHG response [16], significantly
different from many known 2D NLO materials [17–19]. Consequently, ∑ |〈g|μ|m〉|2 |〈m|μ|f 〉|2 ( )
the NbOX2 thin film can be used to design a spontaneous parametric δtp = 8 ( )2 1 + 2cos2 θ
down-conversion quantum light source with a recorded performance. m∕
=g
m∕
=f
Ef
Em − 2 + Γf2

The first step in this paper is to observe the structural properties of ⃒ ⃒

NbOCl2 using a surface distance projection map and three views. Com­ ⃒Δμ ⃒2 |〈g|μ|f 〉|2 ( )
(4)
gf
+ 8 ( )2 1 + 2cos2 φ
bined with a total density of states (TDOS) and photoelectronic spectrum Ef
(PES) analysis to study the electronic structure of NbOCl2. Second, 2
+ Γ2f
methods such as charge density difference (CDD), transition dipole
moment density (TDMD), and one-photon absorption (OPA) are used to where |f〉 represents the final state, |m〉 stands for the intermediate state,
reveal the optical properties of NbOCl2. Third, the two-photon absorp­ 〈g| denotes the ground state, and μ is the electrical dipole moment op­
tion (TPA) characteristics of NbOCl2 materials are studied and analyzed. erators, Ef and Em are energies at the final state and the intermediate
Achieving large and highly adjustable second-order NLO responses, such excited state and, respectively; and Δμgf = 〈g|μ|g〉 − 〈f|μ|f〉 is the differ­
as second harmonic generation (SHG) and bulk photovoltaic effect ence between permanent dipole moments at the excited state and that at
(BPVE), are essential for the development of modern optical and pho­ the ground state; where θ is the angle between the vector 〈g|μ|m〉 and
toelectric devices. 〈m|μ|f〉, and the φ is the angle between the two vectors Δμgf and 〈g|μ|f〉.
This sum-overs-states (SOS) method, which is widely used for calcu­
2. Methods
lating many nonlinear optical properties [30,31].

The first-principles calculations involved in this work are entirely

3. Results and discussion
performed by CP2K [20]. The structures were optimized under PBE
functional [21] and DZVP-MOLOPT-SR-GTH basis set [22] combined
According to the surface distance projection diagram of Fig. 1(a), the
with DFT-D3 correction [23] level. The electronic excitation calcula­
three-dimensional structure of NbOCl2 molecules can be observed. The
tions for the periodic system were performed using the TDDFT method
scale bar indicates that 0.0 represents the surface of the system, and
[24] within the first-principles program CP2K. The calculations
− 3.0 represents a distance of 3.0 perpendicular to the surface of 0.0. As
employed the PBE generalization [25], and the electronic structure was
can be seen from the figure, the Cl atoms are arranged in one plane,
described by the DZVP-MOLOPT-SR-GTH pseudopotential basis set.
while the Nb atoms and the O atoms are arranged in another plane,
During the excitation calculations, the Tamm-Dancoff approximation
which corresponds to the three views in Fig. 1(b–d). In the three views,
(TDA) [26] was employed. In the process of performing TDDFT calcu­
the red ball represents the O atom, the cyan ball represents the Cl atom,
lations, we only set the x and y directions to repeat periodically. It is
and the green ball is the Nb atom. The structure of NbOCl2 exhibits
important to note that CP2K considers only the Gamma point for TDDFT
orthorhombic symmetry in the spatial group Pmm2. It consists of vdW-
calculations. Therefore, to ensure accurate results, we set the lattice
stacked Cl–Nb/O–Cl trilayers (TLs) along the c-axis direction (Fig. 1
dimensions to 23.3 Å in the x direction and 40.1 Å in the y direction
(c)). First-order Peierls distortion along the b-axis results in alternating
[27], providing a sufficiently large lattice in the periodic repetition
short and long Nb− Nb bonds. Moreover, a second-order Peierls distor­
direction.
tion along the a-axis causes Nb atoms to be displaced from the center of
The molecular structure diagram was analyzed by VESTA. Surface
[NbO2Cl4] octahedra towards the corner O atoms. Consequently, two
distance projection map, TDOS, PES, absorption spectrum, CDD, and
unequal Nb–O bond lengths are observed. These findings are consistent
TDMD were obtained using Multiwfn [28]. The CDD diagram depicts the
with the results reported in reference [32].
regions of electron increase and decrease as electrons and holes
Fig. 2(a) is the TDOS of NbOCl2 with a cell expansion of 6 × 6 × 1.
respectively, which can represent the process of electron transfer. The
The horizontal axis coordinates in the figure represent energy (unit eV).
electron-hole density is defined as:
The figure illustrates that the monolayer of NbOCl2 is a semiconductor,
∑( )2 ∑( a )2
ρhole (r) = ωai φi φi − ω′i φi φi which is consistent with the findings reported by Jia et al. using
Heyd− Scuseria− Ernzerhof (HSE) hybrid density functional [33]. Fig. 2
(1)
i→a i←a
∑∑ ∑∑
+ ωai ωaj φi φj −
a a
ω′i ω′j φi φj (b) is the PES of NbOCl2 with a cell expansion of 6 × 6 × 1, where the
i→a j∕
=i→a i←a j∕
=i←a horizontal axis coordinates represent the binding energy (unit eV), and
the vertical axis coordinates are the photoelectronic spectrum intensity
∑( )2 ∑( a )2
ρele (r) = ωai φa φa − ω′i φa φa (unit arb.). PES, which shows the relative energies of occupied molec­
ular orbitals by ionization, the peaks with the lowest binding energies
(2)
i→a i←a
∑∑ ∑∑
+ ωai ωbi φa φb −
a b
ω′i ω′i φa φb around 9.1 eV stand for valence electrons, whereas the peaks with
i→a i→b∕
=a i←a i←b∕
=a higher binding energies stand for core electrons. Fig. 2(c) is the TDOS of
NbOCl2 with a cell expansion of 5 × 5 × 1. Fig. 2(d) is the PES of NbOCl2
where ω is the excitation configuration coefficient, and ω′ is the de- with a cell expansion of 5 × 5 × 1, the peaks with the lowest binding
excitation configuration coefficient. r is the coordinate vector, φ is the energies around 7.6 eV. Fig. 2(e) is a comparison of the TDOS of Fig. 2(a)
orbital wave function, i or j is the occupied orbital label, and a or b is the and (c). The green line represents 5 × 5 × 1 and the blue line represents
empty orbital label. Thus Σ represents every excitation configuration of 6 × 6 × 1. As can be seen in Fig. 2(e), there is a significant size effect.
i→a
the cycle, and Σ represents every de-excitation configuration of the cycle. When the structure is from 5 × 5 × 1 to 6 × 6 × 1, TDOS has a significant
i←a

2
N. Zhang et al.
Fig. 1. (a) Surface distance projection map, molecular structure (b) top view (c) front view (d) side view.
red-shift in the low-energy range and blue-shift in the high-energy
range. The highest peak value of TDOS of 6 × 6 × 1 is twice as large
as the highest peak of 5 × 5 × 1. Fig. 2(f) is a comparison of the PES of
Fig. 2(b) and (d). The green line represents 5 × 5 × 1 and the blue line
represents 6 × 6 × 1. Structure from 5 × 5 × 1 to 6 × 6 × 1, the PES
showed blue-shift, indicating a significant size effect.
Fig. 3(a) is a 6 × 6 × 1 absorption spectrum, showing the absorption
characteristics of NbOCl2 material in the visible range (400–725 nm).
The black curve in the figure represents the total absorption, the red
curve represents the absorption in the Y direction, and the blue curve
represents the absorption in the X direction. The short line on the curve
represents the peak absorption in the corresponding direction. As can be
seen from the figure, the NbOCl2 is anisotropic and has different ab­
sorption peaks in each direction. Fig. 3(b) is a 5 × 5 × 1 absorption
spectrum, which also shows the absorption characteristics of NbOCl2 in
the visible range. Compared with Fig. 3(a), the absorption peak in the
figure has changed, and there are also differences in the absorption peak
in different directions. The total absorption curves of Fig. 3(a) and (b)
were compared, as shown in Fig. 3(c). The purple curve represents the
case where the cell expansion is 6 × 6 × 1, and the green curve repre­
sents the case where the cell expansion is 5 × 5 × 1. Through compar­
ison, it can be found that in the visible range, when the structure is
expanded from 5 × 5 × 1 to 6 × 6 × 1, the strongest absorption peak is
from 409 nm to 445 nm. This shift indicates a significant red-shift in the
absorption spectrum and highlights the evident size effect.
As can be seen from Fig. 3(a), there are five relatively strong peaks in
the absorption spectrum in the visible range, corresponding to five
excited states, S36, S90, S124, S586, and S999. To observe the charge
3
Journal of Molecular Structure 1299 (2024) 137064
transfer of the above five absorption peaks, it is necessary to study the
electron-hole distribution. Therefore, further calculations are made to
obtain the charge density differential [34]. Fig. 4 is the CDD of the
strong absorption peaks S36, S90, S124, S586, and S999 in the absorption
spectrum. The charge transfer of molecules in different excited states,
where purple represents holes and yellow represents electrons. The first
row is a top view, and the second row is a side view of the same excited
state. In Fig. 4(a–e), there are both purple and yellow regions around the
Nb atom. The electrons in Fig. 4 (a–e) are transferred around the Nb
atom, and the holes are transferred around the Cl atom and the O atom.
The different electron-hole distribution leads to different exciton bind­
ing energies [35], as shown in Table 2. In Table 2 the excited state S36 to
S90 and then to S124, the exciton binding energy gradually increases, the
S586 exciton binding energy decreases, and the S999 exciton binding
energy increases again.
Using the transition dipole moment density, the contribution of
various positions in the system to the transition dipole moment can be
easily investigated. As we all know, the oscillator intensity that de­
termines the probability of transition between electronic states is pro­
portional to the square of the modulus of the transition dipole moment.
Fig. 5 is a TDMD of the strong absorption peaks in the absorption
spectrum. Top view showing the transition dipole moment density map
of S36, S90, S124, S586, and S999 respectively. The orange area is the area
where electrons increase, and the blue area is the area where electrons
decrease. In the X and Y directions of S36, S90, S124, S586, and S999, the
regional density follows a periodic trend of decreasing, increasing,
decreasing, and increasing, as shown in Fig. 5 (a–e). Table 1 is the
transition dipole moments for five strong absorption peaks of OPA.
N. Zhang et al.
Fig. 2. DOS and PES. (a) DOS of 6 × 6 × 1, (c) DOS of 5 × 5 × 1, (e) comparison of DOS between 6 × 6 × 1 and 5 × 5 × 1, (b) PES of 6 × 6 × 1, (d) PES of 6 × 6 × 1,
(f) comparison of PES between 6 × 6 × 1 and 5 × 5 × 1.
TPA is a third-order nonlinear optical process that involves the
excitation of molecules by two photons. It is a two-step transition from
the ground state to the intermediate state to the final state and a one-step
transition from the ground state directly to the final state. The OPA
spectrum of NbOCl2 is analyzed in Fig. 6(a), and since the wavelength of
TPA is twice the wavelength of OPA, we also calculated the corre­
sponding TPA spectrum, as shown in Fig. 6(b). The coordinates of the
vertical axis on the left in the figure are the molar absorption coefficient
(unit L/cm/mol), and the coordinates of the vertical axis on the right are
the two-photon absorption cross-section. The black curve is the total
absorption spectrum, the red line is the spectrum of the two-step tran­
sition, and the blue line is the spectrum of the one-step transition. The
4
Journal of Molecular Structure 1299 (2024) 137064
short vertical lines in the figure are the absorption cross-section corre­
sponding to the transition spectrum. The blue line in the figure almost
coincides with the black curve, indicating that the contribution of the
one-step transition of the second term in formula (4) to the TPA process
dominates.
Dynamic polarizability and hyperpolarizability tensors can be seen in
Table 3 and Table 4, respectively, which demonstrates that there are large
nonlinear optical properties. Thus, the TPA spectrum is calculated, seeing
Fig. 6, which reveals that S33 in TPA is of the large cross-section. As can be
seen from Fig. 6(b), the strong absorption peaks in TPA are at 885 nm, 950
nm, and 1160 nm, respectively, and the highest absorption peaks are near
1300 nm. The S33 state at 1300 nm has a large cross-section, so analyze the
N. Zhang et al. Journal of Molecular Structure 1299 (2024) 137064

Fig. 3. OPA of NbOCl2. (a) 6 × 6 × 1, (b) 5 × 5 × 1, (c) comparison between 6 × 6 × 1 and 5 × 5 × 1.

Fig. 4. Charge density difference of OPA. (a) S36, (b) S90, (c) S124, (d) S586, (e) S999.

Fig. 5. Transition dipole moment density of OPA. (a) S36, (b) S90, (c) S124, (d) S586, (e) S999.

5
N. Zhang et al. Journal of Molecular Structure 1299 (2024) 137064

Table 1 characterization methods such as surface distance projection map and

The transition dipole moments (a.u.) for five strong absorption peaks for OPA. three views, TDOS, PES, CDD, TDMD, OPA spectrum, and TPA spectrum.
X Y Z There is a size effect on the DOS, PES, and OPA spectrum, that is, as the
size increases, DOS red-shift, the energy of the highest occupied state is
S36 − 8.6929E− 01 − 5.2439E− 03 9.2331E− 05
S90 − 6.0235E− 03 1.3308E+00 6.3314E− 06 from − 6.2 eV to − 7.5 eV; PES is blue-shift, that is, the energy with the
S124 − 8.3677E− 01 − 2.9383E− 03 2.5870E− 04 lowest binding energy is from 7.6 eV to 9.1 eV; and there is a significant
S586 − 8.7820E− 03 − 1.6023E+00 − 6.5009E− 06 red-shift in OPA spectrum, that is, the absorption peak is from 400 nm to
S999 − 3.9388E− 02 − 5.5916E− 01 1.4821E− 04 450 nm. CDD indicates that there is charge transfer around the Nb atom
of NbOCl2. The exciton binding energy increased from 2.5 eV to 3.3 eV,
then decreased to 2.2 eV, and finally increased to 3.1 eV. There is a
Table 2 periodic change in TDMD. There is a large cross-section in the S33 state
Exciton Binding energy of 5 strong absorption peaks of OPA. near 1300 nm, and the contribution of a one-step transition to two-
hole-electron Coulomb attractive energy (exciton binding energy) photon absorption dominates, indicating that TPA can selectively
S36 2.516158 eV
enhance the light absorption intensity. This paper provides an indepth
S90 2.812138 eV understanding of the optical properties of NbOCl2 and provides a
S124 3.271397 eV theoretical basis for the miniaturization research of quantum light
S586 2.223759 eV sources.
S999 3.095905 eV

CDD diagram of the one-step transition that dominates its excited state
TPA process, as shown in the illustration in Fig. 6(d). The electrons in the
Table 3
illustration are transferred around the Nb atom, and the holes are trans­
Dynamic polarizability tensor, unit au.
ferred around the Cl atom and the O atom. In the OPA spectrum of NbOCl2
XX YY ZZ
(Fig. 6(a)), the wavelengths corresponding to the strong peaks of TPA are
443 nm, 475 nm, 580 nm, and 650 nm, while the strong peaks in the OPA Dynamic polarizability tensors S33 36.96 162.28 3.03
spectrum are at 443 nm and 580 nm, and the absorption peaks at 475 nm
and 650 nm are very small, indicating that TPA can selectively enhance the
light absorption intensity. Table 4
Dynamic hyperpolarizability polarizability tensor, unit au.
4. Conclusion Beta || Beta ||(z) Beta _|_(z)

First dynamic S33 − 974,887.66 368,327.03 122,775.68

In short, this paper mainly studies the linear and nonlinear optical hyperpolarizability tensor
absorption of two-dimensional monolayer NbOCl2 through

Fig. 6. TPA spectrum. (a) OPA spectrum, (b) TPA spectrum, (c) two-step transition, (d) one-step transition.

6
N. Zhang et al.
CRediT authorship contribution statement
Na Zhang: Software, Visualization, Writing – original draft. Ning Li:
Software. Li Wang: Formal analysis. Mengtao Sun: Conceptualization,
Methodology, Funding acquisition. Jingang Wang: Project adminis­
tration, Conceptualization, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
This research was funded by Natural Science Foundation of Liaoning
Province (No. 2022-MS-363) and the basic scientific research level
project of the Education Department of Liaoning Province (No.
LJKMZ20220735).
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