Microwave and ab initio studies of rare gas-methane van der Waals complexes

Rotational spectra of the weakly bound Kr-methane van der Waals complex were recorded using a pulsed molecular beam Fourier transform microwave spectrometer in the range from 3.5 to 18 GHz. Spectra of 25 isotopomers of Kr-methane were assigned and analyzed. For isotopomers containing CH4, 13CH4, and CD4, two sets of transitions with K = 0 and one with K = 1 were recorded, correlating to the j = 0, 1, and 2 rotational levels of free methane, respectively (j is the rotational angular momentum quantum number of the methane monomer). For isotopomers containing CH3D and CHD3, two K = 0 components were recorded, correlating to the j(k) = 0(0) and 1(1) rotational levels of free methane (k corresponds to the projection of j onto the C3 axis of CH3D and CHD3). The obtained spectroscopic results were used to derive van der Waals bond distance R, van der Waals stretching frequency nu(s), and the corresponding stretching force constant k(s). Nuclear spin statistical weights of individual states were obtained from molecular symmetry group analyses and were compared with the observed relative transition intensities. The tentatively assigned j = 2 transitions were more intense than predicted from symmetry considerations. This is attributed to a relatively large effective dipole moment of this state, supported by ab initio dipole moment calculations. Ab initio potential energy calculations of Kr-CH4 and Ar-CH4 were done at the coupled cluster level of theory, with single and double excitations and perturbative inclusion of triple excitations, using the aug-cc-pVTZ basis set supplemented with bond functions. The theoretical results show that the angular dynamics of the dimer does not change significantly when the binding partner of methane changes from Ar to Kr. The dipole moment of Ar-CH4 was calculated at various configurations, providing a qualitative explanation for the unsuccessful spectral searches for rotational transitions of Ar-CH4.     

Effects of torsion on O-H stretch overtone spectra and direct overtone photolysis of methyl hydroperoxide

We use laser photoacoustic spectroscopy to obtain overtone spectra at three through six quanta of O-H stretch excitation (3nu(OH)-6nu(OH)) for methyl hydroperoxide (MeOOH). Extending the spectral regions beyond our previous work reveals new features that can be attributed to transitions involving torsion about the O-O bond. Experimental spectral profiles (3nu(OH)-6nu(OH)) and cross sections (3nu(OH)-5nu(OH)) at room temperature show a good agreement with the simulated spectra that we obtain from ab initio calculations employing a vibration-torsion model at 298 K. A Birge-Sponer analysis yields experimental values for the O-H stretch frequency (omega=3773+/-15 cm(-1)) and anharmonicity (omegax=94+/-3 cm(-1)). We also detect OH radicals by laser-induced fluorescence and present photodissociation action spectra of MeOOH in the regions of 4nu(OH) and 5nu(OH). While the spectral profile at 5nu(OH) mimics the photoacoustic spectrum, the peak intensity for transitions to torsionally excited states is relatively more intense in the action spectrum at 4nu(OH), reflecting the fact that the 4nu(OH) excitation energy is below the literature dissociation energy (D0=42.6+/-1 kcal mol(-1)) so that features in the action spectrum come from thermally populated excited states. Finally, we use our calculations to assign contributions to individual peaks in the room-temperature spectra and relate our findings to a recent dynamics study in the literature.     

IR-UV double resonance spectroscopy of guanine-H2O clusters

We present the IR-UV double resonance spectrum of guanine monohydrate in the region 3100 cm(-1) to 3800 cm(-1) along with the energies and frequencies of these structures calculated at the non-empirical correlated ab initio RI-MP2/cc-pVDZ level. We assign the structures of guanine-water clusters by comparing the experimental spectra with the ab initio calculations and with the IR spectra of the bare guanine monomer. We find two clusters with guanine in the enol-amino tautomeric form and one structure with guanine in the keto-amino form.     

Infrared spectra and ab initio calculations for the Cl--(CH4)n (n = 1-10) anion clusters

In an effort to elucidate their structures, mass-selected Cl--(CH4)n (n = 1-10) clusters are probed using infrared spectroscopy in the CH stretch region (2800-3100 cm(-1)). Accompanying ab initio calculations at the MP2/6-311++G(2df,2p) level for the n = 1-3 clusters suggest that methane molecules prefer to attach to the chloride anion by single linear H-bonds and sit adjacent to one another. These conclusions are supported by the agreement between experimental and calculated vibrational band frequencies and intensities. Infrared spectra in the CH stretch region for Cl--(CH4)n clusters containing up to ten CH4 ligands are remarkably simple, each being dominated by a single narrow peak associated with stretching motion of hydrogen-bonded CH groups. The observations are consistent with cluster structures in which at least ten equivalent methane molecules can be accommodated in the first solvation shell about a chloride anion.     

Harmonic and anharmonic features of IR and NIR absorption and VCD spectra of chiral 4-X-[2.2]paracyclophanes

The vibrational absorption spectra and vibrational circular dichroism (VCD) spectra of both enantiomers of 4-X-[2.2]paracyclophanes (X = COOCD3, Cl, I) have been recorded for a few regions in the range of 900-12000 cm(-1). The analysis of the VCD spectra for the two IR regions, 900-1600 cm(-1) and 2800-3200 cm(-1), is conducted by comparing with DFT calculations of the corresponding spectra; the latter region reveals common motifs of vibrational modes for the three molecules for aliphatic CH stretching fundamentals, whereas in the mid-IR region, one is able to identify specific signatures arising from the substituent groups X. In the CH stretching region between 2900 and 2800 cm(-1), we identify and interpret a group of three IR VCD bands due to HCH bending overtone transitions in Fermi resonance with CH stretching fundamental transitions. The analysis of the NIR region between approximately 8000 and approximately 9000 cm(-1) for X = COOCD3 reveals important features of the aromatic CH stretching overtones that are of value since the aromatic CH stretching fundamentals are almost silent. The intensifying of such overtones is attributed to electrical anharmonicity terms, which are evaluated here by ab initio methods and compared with literature data.     

High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+

The pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of jet-cooled O3 has been recorded in the range 101,000-104,000 cm(-1). The origins of the X 1A1-->X+ 2A1 and X 1A1-->A+ 2B2 transitions could be determined from the rotational structure of the bands, the photoionization selection rules, the photoionization efficiency curve, and comparison with ab initio calculations. The first adiabatic ionization energy of O3 was measured to be 101,020.5(5) cm(-1) [12.524 95(6) eV] and the energy difference between the X+ 2A1 (0,0,0) and A+ 2B2 (0,0,0) states was determined to be DeltaT0=1089.7(4) cm(-1). Whereas the X-->X+ band consists of an intense and regular progression in the bending (nu2) mode observed up to v2+=4, only the origin of the X-->A+ band was observed. The analysis of the rotational structure in each band led to the derivation of the r0 structure of O3+ in the X+ [C2v,r0=1.25(2) A,alpha0=131.5(9) degrees ] and A+[C2v,r0=1.37(5) A,alpha0=111.3(38) degrees ] states. The appearance of the spectrum, which is regular up to 102,300 cm(-1), changes abruptly at approximately 102,500 cm(-1), a position above which the spectral density increases markedly and the rotational structure of the bands collapses. On the basis of ab initio calculations, this behavior is attributed to the onset of large-amplitude motions spreading through several local minima all the way to large internuclear distances. The ab initio calculations are consistent with earlier results in predicting a seam of conical intersections between the X+ and A+ states approximately 2600 cm(-1) above the cationic ground state and demonstrate the existence of potential minima at large internuclear distances that are connected to the main minima of the X+ and A+ states through low-lying barriers.     

Overtone spectroscopy of H2D+ and D2H+ using laser induced reactions

The method of laser induced reaction is used to obtain high-resolution IR spectra of H2D+ and D2H+ in collision with n-H2 at a nominal temperature of 17 K. For this purpose three cw-laser systems have been coupled to a 22-pole ion trap apparatus, two commercial diode laser systems in the ranges of 6100-6600 cm(-1) and 6760-7300 cm(-1), respectively, and a high-power optical parametric oscillator tunable in the range of 2600-3200 cm(-1). In total, 27 new overtone and combination transitions have been detected for H2D+ and D2H+, as well as a weak line in the nu1 vibrational band of H2D+ (2(20)<--1(01)) at 3164.118 cm(-1). The line positions are compared to high accuracy ab initio calculations, showing small but mode-dependent differences, being largest for three vibrational quanta in the nu2 symmetric bending of H2D+. Within the experimental accuracy, the relative values of the ab initio predicted Einstein B coefficients are confirmed.     

Vibrational spectroscopic, first-order hyperpolarizability and HOMO, LUMO studies of 1,2-dichloro-4-nitrobenzene based on Hartree-Fock and DFT calculations

The Fourier-transform infrared spectrum of 1,2-dichloro-4-nitrobenzene (DCNB) was recorded in the region 4000-400cm(-1). The Fourier-transform Raman spectrum of DCNB was also recorded in the region 3500-50cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of DCNB were carried out by ab initio HF and density functional theory (DFT/B3LYP) method with 6-31+G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The values of the total dipole moment (μ) and the first-order hyperpolarizability (β) of the investigated compound were computed using ab initio quantum mechanical calculations. The calculated results also show that the DCNB might have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the infrared and Raman spectra of DCNB is also reported based on total energy distribution (TED). The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The theoretical FT-IR and FT-Raman spectra for the title compound have also been constructed.     

Determination of absolute configuration using concerted ab Initio DFT calculations of electronic circular dichroism and optical rotation: bicyclo[3.3.1]nonane diones

The concerted use of ab initio time-dependent density functional theory (TDDFT) calculations of transparent spectral region optical rotation and of circular dichroism has recently become practicable, permitting the concerted use of transparent spectral region optical rotation and circular dichroism in determining the absolute configurations of chiral molecules. Here, we report concerted TDDFT calculations of the transparent spectral region specific rotations and of the circular dichroism spectra originating in n --> pi C=O group excitations of four bicyclo[3.3.1]nonane diones, 1-4. Comparison to experiment yields absolute configurations for 1-4. For each dione, specific rotations and circular dichroism spectra give identical absolute configurations. Our results are consistent with previous work, with the exception of the Octant Rule-derived absolute configuration of the 2,9-dione.     

A combined ab initio/Franck-Condon study of the A-X single-vibronic-level emission spectrum of CCl2 and the photodetachment spectrum of CCl2 -.

State-of-the-art ab initio calculations have been carried out on the X1A1, ?3B1 and A1B1 states of CCl2 and the X2B1 state of CCl2-. Franck-Condon factors including anharmonicity have been calculated, between the CCl2 states, and between the CCl2- X2B1 state and the CCl2 states. They are used to simulate the A-X single-vibronic-level (SVL) emission spectra of CCl2 determined by M.-L. Lui et al. [PCCP 2003, 5, 352] and the 364 nm laser photodetachment spectrum of CCl2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 1999, 103, 8213]. Comparison between simulated and observed spectra confirms the vibrational assignments of the X2B1 SVL emission spectra and the T0 position of the A1B1 state of CCl2. For the photodetachment spectrum of CCl2-, spectral simulation shows that the higher binding energy ?3B1(CCl2) <-- X2B1(CCl2-) band is well separated from the X1A1(CCl2) <-- X2B1(CCl2-) band. It is concluded that the observed second band, which overlaps heavily with the X1A1(CCl2) <-- X2B1(CCl2-) band in the photodetachment spectrum of CCl2- cannot be assigned to the CCl2(?3B1) + e --> CCl2-(X2B1) detachment process. Further ab initio calculations carried out in the present investigation support the suggestion that the second band in the 364 nm photodetachment spectrum of CCl2- is due to detachment from an excited state of CCl2-, a linear quartet state, to a triplet state of CCl2. These calculations identify the anionic state to be the lowest 4Sigmag- (4Sigma-) state, which photodetaches vertically to the 3Sigmag- (3Sigma-; adiabatically ?3B1) and/or 3Pi(u) (3Pi) states of CCl2 to give the second band observed in the 364 nm photodetachment spectrum of CCl2-.     

Rovibrationally selected and resolved pulsed field ionization-photoelectron study of propyne: ionization energy and spin-orbit interaction in propyne cation

By using a high-resolution infrared (IR) laser to prepare propyne (C(3)H(4)) in selected rotational levels of the excited nu(1) (acetylenic C-H stretching) vibration mode prior to vacuum ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) measurements, we have obtained rotationally resolved VUV-PFI-PE spectra for the C(3)H(4) (+)(X (2)E(32,12),nu(1) (+)=1) band. The analysis of these PFI-PE spectra leads to the determination of the spin-orbit constant of A=-13.0+/-0.2 cm(-1) for the C(3)H(4) (+)(X (2)E(32,12),nu(1) (+)=1) state. Using this A constant and the relative rotationally selected and resolved state-to-state photoionization cross sections thus measured, we have obtained an excellent simulation for the VUV-PFI-PE origin band of C(3)H(4) (+)(X (2)E(32,12)), yielding a value of 83 619.0+/-1.0 cm(-1) (10.367 44+/-0.000 12 eV) for the adiabatic ionization energy of C(3)H(4) [IE(C(3)H(4))]. The present two-color IR-VUV-PFI-PE study has also made possible the determination of the C-H stretching frequencies nu(1) (+)=3217.1+/-0.2 cm(-1) for C(3)H(4) (+)(X (2)E(32,12)). The spectral assignment and simulation were guided by high-level ab initio calculations on the IE(C(3)H(4)), Franck-Condon factors for photoionization transitions, and rotational constants and vibrational frequencies for C(3)H(4) (+).     

Jet cooled spectroscopy of H2DO+: Barrier heights and isotope-dependent tunneling dynamics from H3O+ to D3O+

The first high resolution spectroscopic data for jet cooled H2DO+ are reported, specifically via infrared laser direct absorption in the OH stretching region with a slit supersonic jet discharge source. Transitions sampling upper (0-) and lower (0+) tunneling states for both symmetric (nu1+ <-- 0+, nu1- <-- 0-, and nu1- <-- 0+) and antisymmetric (nu3+ <-- 0+ and nu3- <-- 0-) OH stretching bands are observed, where +/- refers to wave function reflection symmetry with respect to the planar umbrella mode transition state. The spectra can be well fitted to a Watson asymmetric top Hamiltonian, revealing band origins and rotational constants for benchmark comparison with high-level ab initio theory. Of particular importance are detection and assignment of the relatively weak band (nu1- <-- 0+) that crosses the inversion tunneling gap, which is optically forbidden in H3O+ or D3O+, but weakly allowed in H2DO+ by lowering of the tunneling transition state symmetry from D(3h) to C(2v). In conjunction with other H2DO+ bands, this permits determination of the tunneling splittings to within spectroscopic precision for each of the ground [40.518(10) cm(-1)], nu1 = 1 [32.666(6) cm(-1)], and nu3 = 1 [25.399(11) cm(-1)] states. A one-dimensional zero-point energy corrected potential along the tunneling coordinate is constructed from high-level ab initio CCSD(T) calculations (AVnZ, n = 3,4,5) and extrapolated to the complete basis set limit to extract tunneling splittings via a vibrationally adiabatic treatment. Perturbative scaling of the potential to match splittings for all four isotopomers permits an experimental estimate of DeltaV0 = 652.9(6) cm(-1) for the tunneling barrier, in good agreement with full six-dimensional ab initio results of Rajamaki, Miani, and Halonen (RMH) [J. Chem. Phys. 118, 10929 (2003)]. (DeltaV0 (RMH) = 650 cm(-1)). The 30%-50% decrease in tunneling splitting observed upon nu1 and nu3 vibrational excitations arises from an increase in OH stretch frequencies at the planar transition state, highlighting the transition between sp2 and sp3 hybridizations of the OHD bonds as a function of inversion bending angle.     

Conformational stability of cyclobutanol from temperature dependent infrared spectra of xenon solutions, r0 structural parameters, ab initio calculations and vibrational assignment

Variable temperature (-55 to -100 degrees C) studies of the infrared spectra (4000-400 cm(-1)) of cyclobutanol, c-C4H7OH dissolved in liquid xenon have been carried out. The infrared spectrum (4000-100 cm(-1)) of the gas has also been recorded. From these data two of the four possible stable conformers have been confidently identified and their order of stabilities has been experimentally determined where the first indicator is for the position of attachment of the hydroxyl group on the bent cyclobutyl ring (Eq=equatorial or Ax=axial) and the second one (t=trans, g=gauche) is the relative position of the hydroxyl rotor, i.e. rotation around the ring C-O bond. The enthalpy difference between the most stable Eq-t conformer and the second most stable rotamer, Eq-g, has been determined to be 200+/-50 cm(-1) (2.39+/-0.60 kJ/mol). This experimentally determined order is consistent with the order of stability predicted by ab initio calculations Eq-t>Eq-g>Ax-g>Ax-t. Evidence was obtained for the third conformer Ax-g which is predicted by ab initio calculations to be less stable by more than 650cm(-1) than the Eq-t form. The percentage of each conformer at ambient temperature is estimated to be Eq-t (50%), Eq-g (47%) and Ax-g (3%). The conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios and vibrational frequencies have been obtained for all of the conformers from MP2(full)/6-31G(d) ab initio calculations. The optimized geometries and conformational stabilities have been obtained from ab initio calculations utilizing several different basis sets up to MP2(full)/aug-cc-pVTZ and from density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants for the Eq-t conformer combined with ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters have been obtained. The determined heavy atom structural parameters for the Eq-t conformer are: the distances C1-C4=1.547(5) angstroms, C4-C6=1.552(5)angstroms, C-O=1.416(5) angstroms and angles angleC6C4C1=86.6(5) degrees , angleC4C1C5=88.9(5) degrees and angleC6C5C1C4=22.8(5) degrees . The results are discussed and compared to the corresponding properties of some similar molecules.     

Ab initio calculations on low-lying electronic states of TeO2 and Franck-Condon simulation of the (1)1B2 <-- X1A1 TeO2 absorption spectrum including anharmonicity

Ab initio calculations have been carried out on low-lying singlet and triplet states of TeO2 at different levels of theory with basis sets of up to the augmented-polarized valence-quintuple-zeta quality. Equilibrium geometrical parameters, harmonic vibrational frequencies, and relative electronic energies of the X1A1, 1B1, 1B2, 1A2, 3A1, 3B1, 3B2, and 3A2 states of TeO2 have been calculated. Potential energy functions (PEFs) of the X1A1 and the (1)1B2 states were computed at the complete-active-space self-consistent-field multireference configuration interaction level, with a basis set of augmented-polarized valence-quadruple-zeta quality. Franck-Condon factors (FCFs) for the electronic transition between the X1A1 and (1)1B2 states of TeO2 were calculated with the above-mentioned ab initio PEFs. The (1)1B2 <-- X1A1 absorption spectrum of TeO2 was simulated employing the computed FCFs, which include Duschinsky rotation and anharmonicity, and compared with the recently published laser-induced fluorescence (LIF) spectrum of Hullah and Brown [J. Mol. Spectrosc. 200, 261 (2000)]. The ab initio results and spectral simulation reported here confirm the upper electronic state involved in the LIF spectrum to be the (1)1B2 state of TeO2 and also confirm the vibrational assignments of Hullah and Brown. However, our simulated spectrum suggests that the reported LIF spectrum from 345 to 406 nm represents only a portion of the full (1)1B2 <-- X1A1 absorption spectrum of TeO2, which extends from ca. 406 to 300 nm. Another dye other than the two used by Hullah and Brown is required to cover the 345-300 nm region of the LIF band. Ab initio calculations show strong configuration mixing of the (1)1B2 electronic surface with higher 1B2 states in a region of large TeO bond length (> or = 2.0 A) and OTeO bond angle (> or = 135.0 degrees).     

Vibrational assignment of acetylacetone

The infrared and Raman spectra of acetylacetone and its deuterated analogues have been analyzed by the aid of ab initio calculations at post Hartree-Fock level and considering the spectral behavior upon deuteration. By deconvolution of the infrared spectra of acetylacetone and d6-acetylacetone at 1600 cm(-1) region a broad and strong band is found and correlated with the strong Raman lines observed for these compounds in this region. The broadness of this infrared band at room temperature and it's splitting at low temperature is attributed to free rotation of methyl group attached to carbonyl group at room temperature. Furthermore it is found that all ring modes in 1200-1600 cm(-1) region more or less are mixed with the OH in plane bending motion.     

A comparison of experimental and calculated spectra of HNO3 in the near-infrared using Fourier transform infrared spectroscopy and vibrational perturbation theory

This work combines new laboratory studies of the near-infrared vibrational spectra of HNO3 with theoretical predictions of these spectra as a means to understand the properties of this molecule at energies well above the fundamental region. Trends in overtone and combination band energy levels and intensities are compiled and examined. The theoretical calculations are in excellent agreement with the observed frequencies and intensities of the transitions in this spectral region. The calculations also serve as a valuable aid for assigning many of the transitions. This work validates the ab initio generated potential energy surface for HNO3 by comparing vibrational perturbation theory calculations to experimental spectra focused on combination band and overtone absorptions.     

A study of the excited state structure and vibrations of hydroquinone by ab initio calculations and resonant two-photon ionization spectroscopy

Hydroquinone (HYQ) in the lowest electronically excited state has been studied by ab initio quantum chemical calculations and resonant two-photon ionization (R2PI) spectroscopy. Calculations at the MP2/6-31G* and CIS/6-31G* levels yield satisfactory results on structures and vibrational frequencies of the cis-HYQ and trans-HYQ in both the S₀ and S₁ states. Only transitions involving in-plane modes are observed in the R2PI spectrum of HYQ. All spectral bands including some newly observed ones have been successfully assigned with the help of our computed results and analogy with the reported spectra for similar molecules.     

Water line lists close to experimental accuracy using a spectroscopically determined potential energy surface for H2(16)O, H2(17)O, and H2(18)O

Line lists of vibration-rotation transitions for the H(2) (16)O, H(2) (17)O, and H(2) (18)O isotopologues of the water molecule are calculated, which cover the frequency region of 0-20 000 cm(-1) and with rotational states up to J=20 (J=30 for H(2) (16)O). These variational calculations are based on a new semitheoretical potential energy surface obtained by morphing a high accuracy ab initio potential using experimental energy levels. This potential reproduces the energy levels with J=0, 2, and 5 used in the fit with a standard deviation of 0.025 cm(-1). Linestrengths are obtained using an ab initio dipole moment surface. That these line lists make an excellent starting point for spectroscopic modeling and analysis of rotation-vibration spectra is demonstrated by comparison with recent measurements of Lisak and Hodges [J. Mol. Spectrosc. (unpublished)]: assignments are given for the seven unassigned transitions and the intensity of the strong lines are reproduced to with 3%. It is suggested that the present procedure may be a better route to reliable line intensities than laboratory measurements.     

Supersonically cooled hydronium ions in a slit-jet discharge: high-resolution infrared spectroscopy and tunneling dynamics of HD2O+

Jet-cooled high-resolution infrared spectra of partially deuterated hydronium ion (HD2O+) in the O-H stretch region (nu3 band) are obtained for the first time, exploiting the high ion densities, long absorption path lengths, and concentration modulation capabilities of the slit-jet discharge spectrometer. Least-squares analysis with a Watson asymmetric top Hamiltonian yields rovibrational constants and provides high level tests of ab initio molecular structure predictions. Transitions out of both the lower (nu3(+)<--0(+)) and the upper (nu3(-)<--0(-)) tunneling levels, as well as transitions across the tunneling gap (nu3(-)<--0(+)) are observed. The nu3(-)<--0(+) transitions in HD2O+ acquire oscillator strength by loss of D(3h) symmetry, and permit both ground-state-[27.0318(72) cm(-1)] and excited-state-[17.7612(54) cm(-1)]-tunneling splittings to be determined to spectroscopic precision from a single rovibrational band. The splittings and band origins calculated with recent high level ab initio six-dimensional potential surface predictions for H3O+ and isotopomers [X. C. Huang, S. Carter, and J. M. Bowman, J. Chem. Phys. 118, 5431 (2003); T. Rajamaki, A. Miani, and L. Halonen, J. Chem. Phys. 118, 10929 (2003)] are in very good agreement with the current experimental results.     

Laser induced fluorescence and resonant two-photon ionization spectroscopy of jet-cooled 1-hydroxy-9,10-anthraquinone

We carried out laser induced fluorescence and resonance enhanced two-color two-photon ionization spectroscopy of jet-cooled 1-hydroxy-9,10-anthraquinone (1-HAQ). The 0-0 band transition to the lowest electronically excited state was found to be at 461.98 nm (21,646 cm(-1)). A well-resolved vibronic structure was observed up to 1100 cm(-1) above the 0-0 band, followed by a rather broad absorption band in the higher frequency region. Dispersed fluorescence spectra were also obtained. Single vibronic level emissions from the 0-0 band showed Stokes-shifted emission spectra. The peak at 2940 cm(-1) to the red of the origin in the emission spectra was assigned as the OH stretching vibration in the ground state, whose combination bands with the C=O bending and stretching vibrations were also seen in the emission spectra. In contrast to the excitation spectrum, no significant vibronic activity was found for low frequency fundamental vibrations of the ground state in the emission spectrum. The spectral features of the fluorescence excitation and emission spectra indicate that a significant change takes place in the intramolecular hydrogen bonding structure upon transition to the excited state, such as often seen in the excited state proton (or hydrogen) transfer. We suggest that the electronically excited state of interest has a double minimum potential of the 9,10-quinone and the 1,10-quinone forms, the latter of which, the proton-transferred form of 1-HAQ, is lower in energy. On the other hand, ab initio calculations at the B3LYP/6-31G(d,p) level predicted that the electronic ground state has a single minimum potential distorted along the reaction coordinate of tautomerization. The 9,10-quinone form of 1-HAQ is the lowest energy structure in the ground state, with the 1,10-quinone form lying approximately 5000 cm(-1) above it. The intramolecular hydrogen bond of the 9,10-quinone was found to be unusually strong, with an estimated bond energy of approximately 13 kcal/mol (approximately 4500 cm(-1)), probably due to the resonance-assisted nature of the hydrogen bonding involved.