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A theoretical and experimental study of the ethyl-p-aminobenzoate (H2O)n (n =

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JOURNAL OF CHEMICAL PHYSICS VOLUME 113, NUMBER 19 15 NOVEMBER 2000

A theoretical and experimental study of the ethyl-p-aminobenzoate „H2O… n

„ n Ä1 – 4… complexes
José A. Fernández, Asier Longarte, Iñigo Unamuno, and Fernando Castañoa)
Departamento de Quı́mica-Fı́sica, Facultad de Ciencias, Universidad del Pais Vasco, Apartado 644,
48080 Bilbao, Spain
共Received 23 June 2000; accepted 23 August 2000兲
Weakly bound hydrogen bonded ethyl-p-aminobenzoate/water complexes, referred to henceforth
both as EAB/共H2O) n (n⫽1 – 4) or by their stoichiometry 1:n, have been investigated with a
combined approach of mass and light detector laser spectroscopic techniques and ab initio
calculations. The experimental studies follow explorations with laser induced fluorescence 共LIF兲,
and include one-color resonant enhanced multiphoton ionization 共REMPI兲, two-color REMPI
共R2PI兲, pressure dependent R2PI and hole burning 共HB兲 spectroscopies. Calculations were
conducted at the B3LYP/6-31⫹G* level and for the 1:1 complex led to the existence of six stable
isomers, identified as the experimental origin bands at ⫹4, ⫹6, ⫹13, ⫹89, ⫹96, and ⫹108 cm⫺1
above the bare EAB 0 00 transition. It has been shown that three of these bands originate in the EAB
trans conformer, while the other three derive from the EAB gauche conformer. None of the
experimental methods used lead us to observe the EAB共H2O兲2 complex spectrum and the inspection
of the EAB共H2O兲3 REMPI and R2PI spectra has been shown to be a fragmentation from the
EAB共H2O兲4 complex. The structures and identification of the set of isomers are reported and a
comparison with the results on the family complexes methyl-p-aminobenzoate/water is discussed.
© 2000 American Institute of Physics. 关S0021-9606共00兲00643-7兴

I. INTRODUCTION The vibrational and rotationally deep cold molecular beam

The extensive family of weakly bound complexes that
plays an increasingly important role in chemistry, has re-
cently been named1 as ‘‘noncovalent chemistry’’ in contrast
with the ordinary covalent chemistry, where the bonding en-
ergies are several orders higher. Among the ubiquitous
weakly bound species, those held together by a hydrogen
bond have been the subject of considerable research in the
last decades2,3 for two basic reasons: the fundamental and
elusive nature of the hydrogen bonding itself and the appli-
cations to understand the biological processes and the role of
water in nature. Between the weakly bound complexes, those
with hydrogen bonds 共hbonds兲 usually have higher bonding
energies than most others linked by intermolecular forces
and are expected to have medium-shallow potential energy
surfaces, often with several minima 共isomers兲. Often these
properties are difficult to explain by simple computational
methods. At room temperature the molecular components
have total internal energies large enough to split apart most
weakly bound complexes into their components. Only the
complexes fashioned by strong hbonds and to a lesser extent
by strong electrostatic interactions keep small populations at
room temperature, which obviously increase at lower tem-
peratures. Today, the most practical method to achieve sub-
stantial populations of complexes to be easily observed are
the continuous or pulsed supersonic expansions, where a
buffer gas 共typically He兲, seeded with a chromophore and a
solvent at typical stagnation pressures from 1 to 5 bar is
expanded within a vacuum chamber 共at 10⫺8 – 10⫺10 bar).
a兲
Author to whom correspondence should be addressed.
obtained contains large concentrations of an assortment of
complexes, with stoichiometries partially controlled by vary-
ing the solute/solvent ratio.
Once the beam is formed, it is feasible to probe the
mixture of complexes and isomers with a set of complemen-
tary laser spectroscopic techniques 共LIF, REMPI, R2PI, dis-
persed emission 共DE兲, IR–UV double resonance, and oth-
ers兲. The interpretation of the results is crucially aided by ab
initio computation, parametrized potentials, etc. on the iso-
mer binding energies and structures. The ultimate goal is the
identification and the assignment of the isomer structures,
binding energies, and intermolecular vibrations.
Studies of hbond solvation of organic chromophores
with competitive multisite bonding by proton donor or ac-
ceptor water and ammonia–the main concern of this work—
have been the subject of considerable attention.4 The solute–
solvent potential energy hypersurfaces 共PES兲 are prone to be
associated with a considerable number of possible isomers
that in turn, enriches and complicates the study. To charac-
terize and identify the water–chromophore complexes/
isomers the powerful laser techniques must be comple-
mented with extensive ab initio calculations. In a previous
article,5 the methyl-p-aminobenzoate 共MAB兲/water com-
plexes were analyzed by LIF, REMPI, two-color R2PI, fluo-
rescence dispersed emission, and rotational contour resolved
spectroscopy combined with density functional theory 共DFT兲
calculations at the B3LYP/6-31⫹G* level. Three isomers in
the 1:1 complex were identified and their structures well es-
tablished, no 1:2 and 1:3 complexes were observed and only
one isomer was identified for the 1:4 complex.6 In this work,

0021-9606/2000/113(19)/8531/10/$17.00 8531 © 2000 American Institute of Physics

8532 J. Chem. Phys., Vol. 113, No. 19, 15 November 2000
we investigate the water complexes with a multisite hbond
molecule, EAB, with two conformations, gauche and anti, of
the ester ethyl with respect to the benzene ring. The small
energy difference between the bare molecule conformers
共some 175 cm⫺1 at B3LYP/6-31⫹G* level兲7 leads to the
coexistence of both conformers in the supersonic expansions.
In addition, the neighborhood of the CvO and O共Me兲 sol-
vation sites is altered, compared to the MAB. The present
work will address the following questions: is the substitution
in the ester of one methyl group by one ethyl able to change
the relative stability of the EAB/water isomers? Will the sol-
vation change the relative stability of the EAB conformer to
the extent that only complexes originated on one conformer
are observed? Will the attachment of up to four water mol-
ecules to EAB lead to the formation of more than one iso-
mer?
II. PROCEDURES
A. Experimental arrangement
The experimental set up used in this article has been
described earlier5 and only a succinct summary of the tech-
niques will be presented here. One-laser mass-detection ex-
periments, REMPI, and 1⫹1 ⬘ photon absorption, were car-
ried out on a 1.2 m R. M. Jordan TOF, fitted with a heated
stainless-steel Jordan valve and skimmed with a standard 0.8
mm diameter skimmer set at 5 cm from the nozzle. The ions
produced in the crossing of the low temperature
He/MAB/H2O beam with the appropriate synchronized tune-
able laser, were accelerated and sent to the Jordan drift tube
for mass selective detection with a micro channel plates
共MCP兲 detector 共Jordan兲 at the end. Two-laser experiments,
i.e., ‘‘hole burning’’ 共HB兲, R2PI (1⫹1 ⬘ photon absorption兲,
and ionization threshold determination, were also carried out
on an R. M. Jordan TOF by synchronizing the appropriate
pulsed and collimated supersonic beam, the pump XeCl/dye/
frequency doubled coupled laser, and the probe Nd-YAG/
dye/frequency-doubled coupled laser. Pump and probe laser
beams were set in a coaxial counterpropagating configuration
perpendicular to the molecular beam. The ionized species
were accelerated into the TOF drift tube and also detected
with an MCP detector. In both one- and two-laser mass de-
tection experiments the electrical signal from the MCP was
routed to a digital scope 共Tektronix, model TDS520兲 and
further sent to a PC computer for study, analysis, and stor-
age.
Typical stagnation pressures in the adiabatic expansion
were between 1 and 3 bar, while the pressure inside the TOF
spectrometer itself was maintained below 10⫺8 bar. The dyes
used were RD590, DCM, and LDS698. The EAB sample
was heated up to 140 °C in order to get enough sample vapor
concentration in the mixture to yield and study the com-
plexes. Laser wavelengths were calibrated in real time using
a Fizeau wavelength meter 共New Focus, model 7711兲.
B. Theoretical calculations
Quantum chemistry calculations of large-size complexes
共up to 128 electrons兲 require a compromise between both the
theory level and the basis set in order to handle the problem
Fernández et al.
with the desired accuracy. It is well known8 and we have
confirmed it for MAB,9 that DFT yields very accurate struc-
tures and vibrational modes at an affordable computational
cost.10 Accordingly, the calculations reported were carried
out at the Becke3LYP 共B3LYP兲 exchange-correlation
functional,11 with a double-␨ basis set and either with or
without diffuse functions, i.e., 6-31⫹G* and 6-31G basis.12
The latter basis set was the exploring method to examine the
solute–solvent potential energy surface 共PES兲 and the former
as an improved basis set able to describe, among other fun-
damental properties, the pyramidal shape of the NH2 group, a
feature of particular significance in the description of the
isomers geometry and vibrational frequencies of the aniline
derivatives. Owing to the finite nature of the basis set, the
isomers computed energies were corrected for the basis set
superposition error 共BSSE兲 using the full counterpoise
procedure.13 Isomers geometry optimizations were carried
out without constraints and under strict convergence criteria
(opt⫽tight option兲 and the resulting structures checked for
negative frequencies. Binding energies were also corrected
by the zero-point energy 共ZPE兲 and therefore, the values of-
fered in the article are BSSE and ZPE corrected.
The nomenclature employed in the tables to describe the
structures is as follows: the water molecules attached to EAB
are numbered as n 共1 to 4兲, following the order in which they
were added to the bare molecule. Thus, the oxygen atom of
the n-water molecule is labeled as Own (n⫽1 – 4). Hs refers
to the shared proton in a proton–donor water molecule and
Hb to the unshared proton. Owi Ha Ow j is the angle formed by
the O atoms of water molecules i and j at the Ha vertex
共where Ha belongs to water molecule i兲 and Owi Ha ¯Ow j
stand for the hbond distance from the ith water molecule Ha
atom to the oxygen atom of the jth water molecule. The bare
molecule atoms have been labeled as follows:
III. RESULTS
A. Experimental results
1. EAB(H2O)1 complex
The capability of mass-resolved spectroscopy to single
out the spectrum by mass selection has been applied to get
the REMPI spectra at 165, 183, 219, and 237 amu channels,
associated with the 1:0, 1:1, 1:3, and 1:4, and the results are
presented in Fig. 1. As in MAB/water complexes, no 1:2
discrete spectra is observed, in spite of the large wavelength
range scanned. The bare molecule spectrum exhibit the two
0 00 transitions characteristic of the EAB conformers, sepa-
rated by ⬃10 cm⫺1, in good agreement with previous
J. Chem. Phys., Vol. 113, No. 19, 15 November 2000 Ethyl-p -aminobenzoate (H2O) n ( n ⫽1 – 4) complexes 8533

FIG. 2. Set of the five 共A–D, F兲 individual hole burning spectra 共upper
traces兲 and REMPI spectrum 共lower trace兲 of the EAB共H2O兲1 complex. The
low intensity band labeled as E in the REMPI spectrum hampered the scan-
ning of its HB spectrum, but the nonobservation in any other HB spectra
suggest the existence of the sixth isomer.

other REMPI sizable bands match one of the HB spectra, and

hence one can safely conclude that the 1:1 REMPI spectrum
originates in six different isomers. Because of the proximity
of some isomers origin bands and the overlapping of a large
FIG. 1. One-color REMPI spectra of EAB共H2O) n (n⫽0 – 4) complexes as number of vibronic bands, it is not feasible to propose an
obtained in a supersonic expansion of an He/EAB/H2O mixture at a stagna-
assignment of the vibrational bands, as there exist a large
tion pressure of 3 bar. Note the small blue shift of the MAB共H2O兲1 0 00
transition and, in contrast, the large red shift of the MAB共H2O兲4 and number of cross-correlations in the HB traces. Hereafter, the
MAB共H2O兲3 0 00 transitions. six origin bands identified will be labeled as A to F.
It is well established5 that the higher stability of the
isomers/conformers correlates with their REMPI 共LIF兲
observations,14–18 and where the bands at 34 128 and 34 138 higher band intensities, in turn associated with the low rota-
cm⫺1 were assigned to the EAB trans and the EAB gauche tional and vibrational molecular temperatures produced at
origin bands, respectively. high stagnant pressures. As an illustration, in Fig. 3 the
The 1:1 spectrum shows a high vibrational activity, the changes observed in the 0 00 transitions of the EAB共H2O兲1 in
consequence of the superposition of the two EAB conformer the REMPI spectrum recorded at 2 and 5 bar, respectively,
spectra. The reddish peak is shifted ⫹4 cm⫺1 with respect to are shown. It is readily observed that the stagnation pressure
the EAB trans 0 00 transition, a shift similar to that of the increase results in a growth of the B, D, E, and F band
MAB共H2O兲1 Isomer I.5 The close similarity of the 1:3 and
1:4 spectra strongly suggests that the former is due to the
fragmentation of the latter, a hypothesis checked below at
considerably reduced fragmentation in two-color experi-
ments. The 1:4 spectrum also exhibits a rather complex spec-
troscopy, though in this case it is probably caused by an
important vibrational activity.
The number of isomers contributing to the spectrum has
been investigated by hole burning spectroscopy. Comparison
of the 1:1 REMPI spectrum 共lower trace兲 and the set of hole
burning spectra obtained by setting the probe laser at the
more intense lines of the spectrum 共Fig. 2兲 shows that the
bands at ⫹4, ⫹6, ⫹13, ⫹89, and ⫹108 cm⫺1 with respect to
the EAB trans 0 00 transition are distinctive isomer origin
bands. The band at ⫹96 cm⫺1 does not appear in any of the
above spectra and is tentatively assigned to a new
FIG. 3. One-color REMPI spectra of the EAB共H2O兲1 complex as recorded
EAB共H2O兲1 isomer; the low band intensity hampers the at- at stagnation pressures of 5 bar 共upper trace兲 and 2 bar 共lower trace兲, respec-
tainment of an HB spectrum in the usual way. All of the tively. Note the effect of the cooling on the band intensities.
8534 J. Chem. Phys., Vol. 113, No. 19, 15 November 2000 Fernández et al.

FIG. 4. Ionization signal profiles of the MAB共H2O兲1 isomer bands A–D and
F as a function of the ionization laser wave number. The pump laser was set
at the characteristic wavelength of the A–D and F isomer bands. The isomer
ionization energy is the sum of the 0 00 transition energy plus the ionization FIG. 5. Single hole burning spectrum 共upper trace兲 and REMPI spectrum
laser energy threshold. 共lower trace兲 of the EAB共H2O兲4 complex. The small band labeled with an
asterisk does not appear in the HB trace and therefore it is considered as a
low population isomer.

intensities, the B band being the most sensitive to the pres-
sure increase and therefore associated to one of the less
stable isomers, and also suggesting that the A and C bands
are associated to the most stable complexes.
Ionization thresholds of the isomers associated to A, B,
C, D, and F bands have been measured by pump–probe ex-
periments, their traces are shown in Fig. 4, and their ioniza-
tion thresholds collected in Table I. The ionization trace of
the E band could not be recorded because of its low inten-
sity. Four origin bands have I 0 ←S 1 transitions to the blue of
the EAB gauche and EAB trans I 0 ←S 1 transitions, implying
the presence of a proton-donor water. The D band has the
I 0 ←S 1 transition energy slightly shifted to the red of the
parent conformer, suggesting the bonding of a proton-
acceptor water to the chromophore.5 The unique EAB solva-
tion site able to attach a proton-acceptor water is the NH2
group and therefore this is the structure of the D band.
2. EAB(H2O)4 complex
Regardless of the high vibrational activity of the REMPI
spectrum at 237 amu channel, i.e., of the 1:4 complex, it is
originated by one single isomer. Indeed, the HB spectrum
recorded by setting the probe laser at 33 035 cm⫺1 共Fig. 5兲,
i.e., at the 1:4 origin band, accurately matches all the features
of the 1:4 REMPI spectrum, except the band at 33 045 cm⫺1,
labeled with an asterisk in Fig. 5. Although its low intensity
hampered a proper HB study it is suggested to be due to a
less stable 1:4 isomer.
Figure 6 shows the ion-current traces as a function of the
ionization laser wave number, with the pump laser tuned at
33 035 cm⫺1 共1:4 main isomer 0 00 transition兲 observed at 237
amu 共lower trace兲 and at 219 amu 共upper trace兲. At 237 amu,
the sum of the 0 00 transition and the 1:4 I 0 ←S 1 transition
energies 共lower trace兲 yields the 1:4 ionization energy while
at 219 amu it yields the energy necessary to trigger the frag-

TABLE I. 0 00 transition wave numbers and ionization energies of the EAB trans and EAB gauche conformers and five of the six EAB共H2O兲1 isomers
observed. Isomer E low band origin intensity precluded the determination of its ionization energy.

EAB共H2O兲1

EAB trans EAB gauche Isomer A Isomer B Isomer C Isomer D Isomer E Isomer F
⫺1
S 1 ←S 0 /cm 34 128 34 138 34 132 34 134 34 141 34 217 34 224 34 235
I 0 ←S 1 /cm⫺1 29 005 28 975 29 615 29 725 29 625 28 930 ¯ 29 310
I 0 ←S 0 /eV 7.828⫾0.002 7.826⫾0.002 7.907⫾0.02 7.920⫾0.02 7.909⫾0.02 7.832⫾0.02 ¯ 7.882⫾0.02
J. Chem. Phys., Vol. 113, No. 19, 15 November 2000
FIG. 6. Fragmentation signal profile of the MAB共H2O兲4 complex into
EAB共H2O兲3 as a function of the ionization/probe laser wave number 共upper
trace兲; the pump laser was tuned at the EAB共H2O兲4 0 00 transition. Lower
trace: ionization signal profile of the MAB共H2O兲4 complex a function of the
ionization/probe laser wave number.
mentation process: EAB共H2O) 4* ⫹h ␯ →EAB共H2O兲⫹ 3 ⫹H2O
共upper trace兲. As observed, the 1:4 complex has an I 0 ←S 1
transition energy ⬃2000 cm⫺1 lower than that of the bare
molecule (33 035⫹27 400 cm⫺1 or 7.522 eV兲. The differ-
ence between fragmentation and ionization energy thresholds
is 2390 cm⫺1 and corresponds to the energy required for the
evaporation of one water molecule from the EAB共H2O兲⫹ 4 ably due to a decrease of the ionization energies in high
ion.19
Once the ionization energy is known it is easy to scan
the two-color R2PI spectrum, reducing the possible fragmen-
tation from higher-order complexes. Figure 7 shows the
FIG. 7. R2PI spectrum of the EAB共H2O兲4 complex. The spectra were ob-
tained in a pulsed supersonic expansion of He/EAB/H2O mixture at a stag-
nation pressure of 4 bar.
Ethyl-p -aminobenzoate (H2O) n ( n ⫽1 – 4) complexes 8535
FIG. 8. Schematic drawings of the EAB trans(H2O兲1 isomers as calculated
by DFT methods at the B3LYP/6-31⫹G* level. Details of the isomer sta-
bilization energies, bond distances, and angles are specified in Table II.
R2PI spectrum of EAB共H2O兲4, recorded with the ionization
laser tuned at 29 200 cm⫺1. As expected, the spectrum shown
in Fig. 7 is similar overall to that of REMPI 共Fig. 1兲, with a
considerably reduced, but not negligible, background, prob-
water content stoichiometric complexes. It is also worth not-
ing that the blue part of the R2PI spectrum shows less in-
tense bands than that of the REMPI, a consequence of laser
energy saturation.20–23
B. Calculations
1. EAB(H2O)1 complex
The EAB molecule has five hbond solvation sites: the
CvO lone pairs, the O–共Et兲 group, the aromatic ring
␲-electronic cloud, the NH2 hydrogen atoms, and the amino
N atom. In a previous work,5 it was shown that the
␲-electronic cloud produces low stable complexes, with
higher energy than other hbonds. The other four binding
sites’ stability were examined by computation at the
B3LYP/6-31⫹G* level and the resulting structural param-
eters and binding energies are pictorially depicted in Figs. 8
and 9 and in Tables II and III, respectively. The computed
structures are labeled as isomers I to V followed by a t or a
g referring to the EAB trans or gauche precursor; single
Latin numeral refers to both trans and gauche isomers. Iso-
mers It and Ig have the water hbonded to the CvO group, at
8536 J. Chem. Phys., Vol. 113, No. 19, 15 November 2000
FIG. 9. Schematic drawings of the EAB gauche(H2O兲1 isomers as calcu-
lated by DFT methods at the B3LYP/6-31⫹G* level. Details of the isomer
stabilization energies, bond distances, and angles are shown in Table III.
(Ow )Ha ¯O distances of 1.893 and 1.888 Å and at Ow Ha O
angles of 174.8° and 172.8°, respectively, with binding en-
ergies of 1482 and 1388 cm⫺1 and are the most stable iso-
mers computed. In the determination of the absolute bond
energy of the 1:1 isomers, one should keep in mind that
those derived from the EAB gauche must be diminished by
175 cm⫺1, the energy difference between the EAB trans and
the EAB gauche conformers. The water molecule also inter-
acts with one of the ethyl hydrogens but at a farther distance
共2.870 Å for the isomer IIt and 2.669 Å for the IIg).
In contrast, isomers IIt and IIg are the less stable calcu-
lated structures and correspond to isomers with the proton-
donor water bonded to the O共–Me兲 group, at distances of
2.011 and 1.976 Å, and Ow Ha O angles of 169.5° and 167.4°,
respectively. There also exists an additional interaction of the
water with one of the – CH3 hydrogens found to be at dis-
tances of 2.750 and at 2.975 Å, respectively. The calculated
binding energies are of 434 cm⫺1 for Isomer IIt and of 486
cm⫺1 for isomer IIg.
Isomers III and IV both have the proton-acceptor water
alternatively hbonded to one of the NH2 hydrogen atoms and
are experimentally indistinguishable, and hence named as
one single isomer, i.e., either III/IVt or III/IVg. These struc-
tures are second in stability to isomer I 共isomer IIIt 1087
cm⫺1, IVt 1111 cm⫺1, IIIg 1065 cm⫺1, and IVg 1078 cm⫺1兲
and as in the case of isomer I, the trans core isomers have
slightly larger binding energies than those of the gauche.
Bond distances are very similar for isomers IIIt and IIIg,
2.025 Å, and for isomer IVt and IVg, 2.028 Å, evidencing
Fernández et al.
the very small influence of the ethyl group conformation on
the distant NH2 site of the molecule.
Finally, isomer V structure has the proton-donor water
bonded to the amino nitrogen and the amino lone pair delo-
calized by the entire molecular ␲-frame, so that the NH2
moiety is not prone to accept protons, and in consequence
isomer V is less stable than isomer III/IV. The isomer Vt
calculated binding energy is 868 cm⫺1, while that of isomer
Vg is 844 cm⫺1. The bond distances and angles are of the
same order as those computed for other isomers 共see Tables
II and III兲.
2. EAB(H2O)4 complex
As it will be discussed later and based on the similarity
to MAB共H2O兲4 analogy,5–7 the most likely EAB共H2O兲4
structure has, presumably, a chain of four water molecules
clamped to the NH2 group, with ends linked to one amino
hydrogen and the nitrogen atom 共Fig. 10 and Table IV兲, and
hence only this structure has been considered as the most
stable in the computations. Figure 10 depicts a comparison
between EAB共H2O兲4 trans and gauche calculated structures,
and Table IV collects their most characteristic structural pa-
rameters. The calculation shows that both conformers have a
similar stability, the isomer 1:4g binding energy being 50
cm⫺1 higher than that of 1:4t. However, as has already been
pointed out, the EAB trans conformer is 175 cm⫺1 more
stable than the EAB gauche, and although the 1:4t isomer is
still more stable than the 1:4g the difference is marginal, in
fact smaller than the BSSE correction, so that the calculated
energy is not reliable to assign the experimental spectra to
the calculated structures.
Tables II and III show that the water ring hbond dis-
tances are shorter than those of the 1:1 isomers, probably due
to a cooperative effect with other hbonds. It is also notice-
able that the Ow – Ha (¯Ow ) bond distances, where Ha is the
shared proton, are larger by ⬃0.026 Å than those of Ow – Hb
bonds. Similarly, the 1.012 Å N11–H12 bond distance of the
bare molecule stretches to 1.029 Å, and the C6–N11 bond
distance increases from the 1.390 Å of the bare molecule to
1.408 Å in the complex. Therefore, the presence of the
hbond changes the bare molecule structure in the neighbor-
hood of the solvation site by reducing the strength of some of
its bonds, although the effect does not extend farther away
than two bonds and therefore, the ring parameters are unaf-
fected.
IV. DISCUSSION
The comparison of the EAB共H2O兲1 and the MAB共H2O兲1
spectra5 shows that the existence of two EAB conformers
splits each complex original MAB band into two, i.e., the
three MAB共H2O兲1 origin bands at ⫹3, ⫹85, and ⫹102 cor-
relate with six EAB共H2O兲1 0 00 transitions. Regarding EAB
trans and gauche 0 00 transitions as a reference, the C, E, and
F bands exhibit blue shifts of ⫹3, ⫹85, and ⫹97 cm⫺1 with
respect to the EAB gauche 0 00 transition, while the A, B, and
D bands are blue shifted by ⫹4, ⫹6, and ⫹89 cm⫺1 with
respect to the EAB trans 0 00 transition. Therefore, by analogy
with the MAB共H2O兲1 isomers assignment, the A and C bands
J. Chem. Phys., Vol. 113, No. 19, 15 November 2000 Ethyl-p -aminobenzoate (H2O) n ( n ⫽1 – 4) complexes 8537

TABLE II. Structural parameters of EAB trans conformer and its family of EAB共H2O兲1 complexes, calculated
at the B3LYP/6-31⫹G* level. The atom labeling follows the scheme given in Sec. II B. Bond distances are in
Å, bond angles in degrees, and binding energies in cm⫺1.

EAB trans 共H2O兲1

t-EABa Isomer It Isomer IIt Isomer IIIt Isomer IVt Isomer Vt

C1C2 1.405 1.405 1.406 1.406 1.406 1.404

C2C4 1.388 1.388 1.387 1.387 1.387 1.390
C4C6 1.409 1.410 1.410 1.413 1.412 1.406
C2H7 1.086 1.085 1.086 1.086 1.086 1.086
C4H9 1.088 1.088 1.088 1.087 1.088 1.088
C6N11 1.390 1.387 1.387 1.380 1.380 1.407
N11H12 1.012 1.012 1.012 1.016 1.011 1.016
N11H13 1.012 1.012 1.012 1.011 1.016 1.016
C1C14 1.481 1.478 1.480 1.478 1.478 1.485
C14O15 1.221 1.227 1.218 1.222 1.221 1.220
C14O16 1.357 1.346 1.366 1.360 1.360 1.355
O16C17 1.446 1.453 1.456 1.444 1.444 1.448
C17H18 1.095 1.094 1.095 1.095 1.095 1.095
C17H19 1.095 1.094 1.093 1.095 1.095 1.095
C17C20 1.518 1.517 1.518 1.518 1.518 1.518
C20H21 1.096 1.096 1.096 1.097 1.097 1.096
C20H22 1.096 1.095 1.096 1.095 1.096 1.095
C1C2C4 121.0 121.0 121.0 121.1 121.0 120.8
C2C4C6 120.5 120.5 120.5 120.6 120.6 120.3
C6N11H12 116.7 117.1 117.2 118.5 118.5b 114.3
H12N11H13 112.9 113.2 113.3 114.6 114.5 110.2
O15C14O16 122.6 123.0 122.2 122.3 122.3 122.9
C14O16C17 116.3 117.3 116.2 116.2 116.2c 116.3
O16C17H18 108.7 108.7 108.2 108.8 108.8 108.6
O16C17H19 108.7 108.7 108.1 108.7 108.8 108.6
O16C17C20 107.6 107.4 107.9 107.6 107.6 107.6
C17C20H21 109.6 109.3 109.1 109.7 109.7 109.6
C17C20H22 111.1 111.1 111.0 111.0 111.0 111.1
C17C20H23 110.9 111.2 111.5 111.0 111.1 111.1
H12N11C6C4d ⫺25.1 ⫺21.6 ⫺21.5 ⫺19.6 ⫺19.3c ⫺26.2
OW HA 0.969 0.978 0.974 0.970 0.969 0.980
OW HB 0.969 0.968 0.968 0.970 0.969 0.968
HA OW HB 105.49 105.6 105.4 106.0 106.0 106.0
Hbond angle 174.8 169.5 176.6 176.8 161.8
Hbond distance 1.893 2.011 2.025 2.028 2.012
Binding energy/cm⫺1e 1482 434 1087 1111 868
a
Bare EAB trans molecule parameters.
b
C6N11H13.
c
H13N11C6C5.
d
Dihedral angles.
e
Corrected from ZPE and BSSE.

are identified as isomers It and Ig, the D and E bands to
isomers III/IVt and III/IVg, and the B and F to isomers IIt
and IIg. The results lead to the conclusion that the substitu-
tion of the ester methyl by ethyl has a minor effect on the
environment of the NH2 solvation site. The identification is
also in agreement with the stability patterns observed in the
spectra recorded as a function of the stagnant pressure, and is
further confirmed by the ionization energies. In fact, the D
band shows an I 0 ←S 1 transition energy red-shifted with re-
spect to that of the bare molecule, implying that the water is
a proton acceptor. In this case, the bare molecule electron
density decrease in the ion should be mirrored with an in-
crease of the sharing of the proton with the water molecule
and as a consequence, the complex-ion binding energy
should be larger than that of the complex excited state.
The substitution of the ester methyl by ethyl does not
perturb the CvO solvation environment, as the water mol-
ecule senses the pair of hydrogen atoms about the same in
either MAB or EAB. As the solvation site neighborhood
does not change substantially with the substitution, there is
not an appreciable change in binding energy or in the 0 00
transition shift.
Only the band assigned to isomer IIt changes from ⫹102
cm⫺1 to ⫹6 cm⫺1 going from MAB to EAB and its com-
puted structure 共Fig. 8兲 shows a close water molecule to the
ethyl hydrogens in EAB共H2O兲1. The closest distance of the
water molecule to the aromatic ring in isomer IIt is 3.160 Å
(Ow ¯H10) diminishing to 2.829 Å in the MAB共H2O兲1 iso-
mer II; in addition the Ow ¯HCH2 calculated distance is
3.095 Å for MAB共H2O兲1 isomer II and only 2.829 Å for
EAB共H2O兲1 isomer IIt. Therefore an inversion in the relative
weight of the water–alkylic and water–ring interactions has
been produced going from MAB共H2O兲1 to EAB共H2O兲1 iso-
mer IIt. As the interaction of the water molecule with the
8538 J. Chem. Phys., Vol. 113, No. 19, 15 November 2000 Fernández et al.

TABLE III. Structural parameters of the EAB gauche conformer and its family of EAB共H2O兲1 complexes,
calculated at the B3LYP/6-31⫹G* level. The atom labeling follows the scheme given in Sec. II B. Distances
are in Å and energies in cm⫺1. Note that the EAB gauche conformer is 175 cm⫺1 less stable than the EAB trans
conformer and therefore that amount should be subtracted from the binding energies when compared to those of
the EAB trans parent complexes.

EAB gauche 共H2O兲1

a
EAB-g Isomer Ig Isomer IIg Isomer IIIg Isomer IVg Isomer Vg

C1C2 1.405 1.405 1.406 1.406 1.406 1.404

C2C4 1.388 1.387 1.387 1.387 1.387 1.390
C4C6 1.409 1.410 1.410 1.413 1.412 1.406
C2H7 1.086 1.085 1.086 1.086 1.086 1.086
C4H9 1.088 1.089 1.088 1.087 1.088 1.088
C6N11 1.390 1.387 1.387 1.380 1.380 1.407
N11H12 1.012 1.012 1.012 1.016 1.011 1.016
N11H13 1.012 1.012 1.012 1.011 1.016 1.015
C1C14 1.481 1.478 1.479 1.478 1.478 1.485
C14O15 1.221 1.228 1.218 1.222 1.221 1.220
C14O16 1.358 1.347 1.368 1.361 1.360 1.356
O16C17 1.448 1.455 1.457 1.446 1.444 1.450
C17H18 1.093 1.093 1.092 1.094 1.095 1.093
C17H19 1.093 1.092 1.092 1.093 1.095 1.093
C17C20 1.522 1.521 1.521 1.522 1.518 1.522
C20H21 1.098 1.096 1.097 1.097 1.097 1.097
C20H22 1.094 1.094 1.094 1.094 1.096 1.094
C1C2C4 121.0 121.0 121.0 121.1 121.0 121.0
C2C4C6 120.5 120.5 120.5 120.6 120.7 120.3
C6N11H12 116.7 117.2 117.1 118.5 118.4b 114.4
H12N11H13 112.9 113.2 113.2 114.6 114.5 110.3
O15C14O16 123.0 123.5 122.3 122.7 122.3 123.2
C14O16C17 117.1 118.5 117.0 117.1 116.2c 117.2
O16C17H18 104.1 103.6 104.0 104.1 104.1 104.0
O16C17H19 108.8 109.2 108.5 108.8 108.8 108.8
O16C17C20 111.5 111.4 111.2 111.6 107.6 111.4
C17H20H21 109.6 109.2 109.4 109.7 109.7 109.6
C17H20H22 110.9 111.2 111.1 110.9 111.0 111.0
C17C20H23 110.9 110.9 110.9 110.9 111.1 111.0
H12N11C6C4d ⫺25.2 21.6 21.7 18.8 ⫺19.3c 28.7
OW HA 0.969 0.979 0.974 0.969 0.969 0.980
OW HB 0.969 0.968 0.968 0.969 0.969 0.968
HA OW HB 105.49 105.7 105.6 106.0 106.0 105.9
Hbond angle 172.8 167.4 176.2 176.7 164.5
Hbond distance 1.888 1.976 2.025 2.028 2.010
Binding energye 1388 486 1065 1078 844
a
Bare EAB gauche molecule.
b
C6N11H13.
c
H13N11C6C5.
d
Dihedral angles.
e
Corrected from ZPE and BSSE.

ring is the cause of the shift—the alkylic moiety of the mol-
ecule is not affected by the electronic excitation—the large
shift observed on MAB is considerably reduced in the
EAB共H2O兲1 IIt. In contrast, the 1:1g shift 共⫹97 cm⫺1兲 is
not far from that observed for MAB共H2O兲1. Observation of
the isomer IIg structure shows that the water–alkylic group
distance is 2.975 Å, while the interaction with the closest
ring hydrogen atom is 2.874 Å, values closer to those calcu-
lated for MAB共H2O兲1 isomer II. Therefore, it is plausible to
suggest a correlation between the water–ring interaction dis-
tance and the complex 0 00 transition shift.
The pattern of unobserved spectra for the EAB共H2O兲2
and EAB共H2O兲3 species has also been observed for the
MAB/water and MAB/ammonia systems and attributed to
the existence of electronic dark states. In addition,
EAB共H2O兲4 and MAB共H2O兲4 have a very close spectral be-
havior: their 0 00 transitions are red-shifted by ⫺1093 cm⫺1
for the former compared to ⫺1134 cm⫺1 in the MAB com-
plex, and the I 0 ←S 1 transition is shifted to the red in both
cases by ⬃2000 cm⫺1 with respect to the bare molecule, and
even the spectrum vibrational features look very much alike.
Therefore, instead of examining the possible solvation sites
for a four-water chain, only the structures shown in Fig. 9
were calculated, and the results obtained match the structures
calculated for MAB共H2O兲4 and the experimental results very
well. From the data depicted in Table IV it is inferred that
both trans and gauche core structures are very similar, and
most parameters are equal to the third significant figure. The
calculated binding energies are almost coincident and their
J. Chem. Phys., Vol. 113, No. 19, 15 November 2000 Ethyl-p -aminobenzoate (H2O) n ( n ⫽1 – 4) complexes 8539

TABLE IV. Binding energy in cm⫺1 and structural parameters of the

EAB共H2O兲4 complex, as calculated at the B3LYP/16-31⫹G* level. Bond
distances are given in Å, bond angles in degrees, and binding energies in
cm⫺1. To compare the stability of EAB trans and EAB gauche based iso-
mers, it is necessary to add 175 cm⫺1 to the parent EAB gauche isomers.

EAB共H2O兲4

trans gauche

C1C2 1.404 1.403

C2C3 1.390 1.390
C3C4 1.406 1.406
N–H 1.029 1.029
CvO 1.220 1.220
C–N 1.409 1.408
Ow1 – Ha 0.991 0.991
Ow1 – Hb 0.968 0.968
Ow2 – Ha 0.993 0.992
Ow2 – Hb 0.968 0.968
FIG. 10. Two view drawings of the MAB trans(H2O兲4 and MAB
Ow3 – Ha 0.992 0.991
gauche(H2O兲4 isomers as calculated by DFT methods at the
Ow3 – Hb 0.968 0.968
B3LYP/6-31⫹G* level. Details of the isomer stabilization energies, bond
Ow4 – Ha 0.994 0.994
distances, and angles are specified in Table IV.
Ow4 – Hb 0.968 0.968
C1C2C3 120.8 120.8
C2C3C4 120.5 120.4
C3C4C5 118.9 118.9
differences are within the BSSE limits. Therefore, one con- Ha Ow1 Hb 106.1 106.1
cludes that the relative orientation of the ethyl group has Ha Ow2 Hb 105.7 105.8
little influence on the NH2 solvation site. The calculated Ha Ow3 Hb 106.0 106.0
binding energies are not by themselves strong enough evi- Ha Ow4 Hb 106.0 106.7
Ow1 ¯H–N 1.893 1.888
dence to identify the two origins in the EAB共H2O兲4 spec-
Ow1 Ha ¯Ow2 1.752 1.751
trum. However, the observed shift between both 0 00 transi- Ow2 Ha ¯Ow3 1.738 1.739
tions is ⬃10 cm⫺1, reproducing the splitting between EAB Ow3 Ha ¯Ow4 1.742 1.743
trans and gauche conformers, indicating that probably the Ow4 Ha ¯N 1.866 1.867
origin band most to the red corresponds to the EAB共H2O兲4 Ow1 HN 176.8 176.6
Ow1 Ha Ow2 175.7 176.0
trans core isomer, while the origin band most to the blue
Ow2 Ha Ow3 175.7 175.6
共and less intense兲 is due to the EAB共H2O兲4 gauche core iso- Ow3 Ha Ow4 177.5 177.7
mer. The intensity patterns of both origins suggests a some- Ow4 Ha N 175.6 175.1
what larger difference in binding energies, but still of the Binding energya 8174 8224
order of what has been calculated and what has been found a
Corrected by BSSE and ZPE.
for the bare molecule.

band is assigned to the parent EAB共H2O兲4 trans isomer,

V. SUMMARY
The spectroscopy of EAB共H2O) n , n⫽1 – 4 has been in-
vestigated by a variety of mass-resolved experimental tech-
niques, and the results rationalized with the aid of ab initio
calculations at B3LYP/6-31⫹G* level. Six different isomers
are found for the 1:1 complex, with 0 00 transitions, three with
the EAB trans core, and the other three with the EAB
gauche one. The isomers’ shifts resemble that of MAB/water
system 关⫹3, ⫹85, and ⫹97 cm⫺1 for the gauche-core iso-
mers and ⫹4, ⫹6, and ⫹89 cm⫺1 for the trans-core isomers,
compared with ⫹3, ⫹85, and ⫹102 cm⫺1 for MAB共H2O兲1兴.
Only the band associated to isomer IIt exhibits an unex-
pected small blue shift. A change of the geometry of the
complex, a consequence of the interaction of the solvent with
the alkyl group of the molecule, seems to be the cause of the
blue shift.
Two isomers have been found for EAB共H2O兲4, one of
them with a very small 0 00 transition, with shifts of ⫺1093
and ⫺1083 cm⫺1, respectively. Based on the observed shifts
and on the calculated structures’ stabilities, the lower energy
while the high energy band is assigned to the parent
EAB共H2O兲4 gauche isomer.
The observed shifts and the calculated structures lead to
the conclusion that the substitution of the ester methyl by the
ethyl group only affects the O共Et兲 solvation site.
ACKNOWLEDGMENTS
We are grateful to DGES 共Grant Nos. PB95-0510,
PB96-1472兲, DPC 共Basque Government, cofinanced Grant
No. PB96-1472兲, and to UPV for the generous support with
the equipment and running expenses. J.A.F. thanks the MEC
for the award of a postdoctoral contract to carry out work
with Dr. M. N. Sánchez and Dr. F. Castaño. A.L. and I.U.
thank the Basque Government for their fellowships.
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