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Benderskiĭ, V. A.; Vetoshkin, E. V.; Irgibaeva, I. S.; Trommsdorff, H.P.

doi:10.1023/a:1014025916478

Cited by 16 publications

(21 citation statements)

References 30 publications

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“…Relation (14) shows that Fermi interaction equalizes tunneling splittings and, consequently, band intensities of longitudinal and transverse vibrations. Both parameters (An~ and Fn~.)…”

Section: (~4)mentioning

confidence: 99%

“…Far beyond these regions the contributions of several states with different n' values become significant, so the two-level system approximation leading to Hamiltonian (14) is no longer valid. Fermi resonances affect tunneling splittings, causing, in particular, an anomalous isotope effect, i.e., increase in the tunneling splittings in excited states upon replacement of a light isotope by a heavy one, due to change in the frequencies of resonant states.…”

Section: (~4)mentioning

confidence: 99%

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Tunneling dynamics of internal rotation in the nitric acid molecule

Benderskiĭ

Vetoshkin

1999

Russ Chem Bull

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The Hamiltonian of internal rotation about the 6'., axis in the HNO 3 molecule and its H/D-, OI~/O 16-, and NtS/N14-isotopomers was reconstructed using the results of quantumchemical calculations. The Fermi resonance between the torsional (2v 9) and ONO bending (v5) vibrations is a characteristic feature of the molecule. Tunneling splittings in the ground and excited states were calculated using the perturbative instanton approach. Abnormally large changes in the splittings upon isotope substitution of heavy atoms are predicted.Key words: nitric acid, potential energy surface, internal rotation, tunneling splittings.Intensive experimental studies of internal rotation in the nitric acid molecule were carried out in the 1950--1960s. The structure of the molecule was determined from microwave spectra. 1 Detailed study z of vibrational spectra of its H-, D-, taN-, and 15N-isotopomers showed that hindered internal rotation of the OH group, corresponding to the torsional vibration in planar stable configurations, occurs in the HNO 3 molecule. A salient feature of this molecule is resonance between the torsional and ONO bending vibrations, which is responsible for the fact that tunneling splitting of the ONO bending vibration in the first excited state (35.5 MHz) is comparable with that of the second level of torsional vibration (50:7 MHz) and far (by some orders of magnitude) exceeds the splittings of the zero (-3 kHz) and first (-2 MHz) levels of the latter. 3-7The aim of this work is to carry out a theoretical study of the HNO 3 molecule and its isotopomers. Tunneling splittings found for the ground and lowest excited states are in good agreement with experimental data. Changes in tunneling splittings upon isotope substitution of H (by D) and heavy nuclei are considered and anomalous isotope effects are predicted. A universal approach to description of multidimensional tunneling dynamics, called the perturbative instanton approach (PIA), has been reported earlier, s-t4The PIA considers tunneling dynamics in low-energy potential energy surfaces (PES) of a rather general type. The PES is constructed using 3N -6 generalized reactive coordinates (i.e., a totality of generalized coordinates including the coordinate of transition between stable configurations) and includes (1) a one-dimensional (1 D) potential for the angular-tunneling coordinate 0 and (2) a set of small-amplitude transverse coordinates (coupled with r whose frequencies, equilibrium positions, and anharmonicities depend on 0. Despite the relatively simple structure, such PES provide the possibility of performing calculations with a desired accuracy in the low-energy region.

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“…Relation (14) shows that Fermi interaction equalizes tunneling splittings and, consequently, band intensities of longitudinal and transverse vibrations. Both parameters (An~ and Fn~.)…”

Section: (~4)mentioning

confidence: 99%

Section: (~4)mentioning

confidence: 99%

Tunneling dynamics of internal rotation in the nitric acid molecule

Benderskiĭ

Vetoshkin

1999

Russ Chem Bull

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“…Proton transfer is one of the most important and ubiquitous reactions in both chemistry and biology and has been widely studied. [21][22][23][24][25][26] Most theoretical studies have focused on tunneling splitting in the ground state, [27][28][29][30][31][32][33][34][35][36][37] but proton transfer in electronically excited states has also been studied. [38][39][40][41][42][43][44] Spectroscopic studies of the real-time dynamics of proton transfer have been limited, to our knowledge, to excited electronic states.…”

Section: Introductionmentioning

confidence: 99%

Time-resolved photoelectron spectroscopy of proton transfer in the ground state of chloromalonaldehyde: Wave-packet dynamics on effective potential surfaces of reduced dimensionality

Varella

Arasaki

Ushiyama

et al. 2006

The Journal of Chemical Physics

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We report on a simple but widely useful method for obtaining time-independent potential surfaces of reduced dimensionality wherein the coupling between reaction and substrate modes is embedded by averaging over an ensemble of classical trajectories. While these classically averaged potentials with their reduced dimensionality should be useful whenever a separation between reaction and substrate modes is meaningful, their use brings about significant simplification in studies of time-resolved photoelectron spectra in polyatomic systems where full-dimensional studies of skeletal and photoelectron dynamics can be prohibitive. Here we report on the use of these effective potentials in the studies of dump-probe photoelectron spectra of intramolecular proton transfer in chloromalonaldehyde. In these applications the effective potentials should provide a more realistic description of proton-substrate couplings than the sudden or adiabatic approximations commonly employed in studies of proton transfer. The resulting time-dependent photoelectron signals, obtained here assuming a constant value of the photoelectron matrix element for ionization of the wave packet, are seen to track the proton transfer.

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“…Proton tunneling in typical polyatomic molecules has been well understood by combining spectroscopic measurement of the tunneling splittings [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] with theoretical studies on tunneling potentials. [15][16][17][18][19][20][21][22][23][24][25] The ⌬ 0 Ј -⌬ 0 Љ values of TRN and 9HPO measured for the isolated molecules and in the condensed phase are substantially different. For example, the ⌬ 0 Ј -⌬ 0 Љ values of TRN and deuterated TRN͑OD͒ measured in a neon matrix are 21 and 7 cm Ϫ1 , 4 respectively, while the corresponding values are 18.9 and 2.2 cm Ϫ1 for the isolated molecules.…”

Section: Introductionmentioning

confidence: 99%

“…16,20,[22][23][24] Such multidimensional models have not a͒ Present address: Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-Park, Fukuoka 816-8580, Japan.…”

Section: Introductionmentioning

confidence: 99%

Effects of intermolecular interaction on proton tunneling: Theoretical study on two-dimensional potential energy surfaces for 9-hydroxyphenalenone-CO2/H2O complexes

Mori

Sekiya

Miyoshi

et al. 2003

The Journal of Chemical Physics

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Theoretical studies of the N2O van der Waals dimer: Ab initio potential energy surface, intermolecular vibrations and rotational transition frequencies Role of isomerization channel in unimolecular dissociation reaction H 2 CO→H 2 +CO : Ab initio global potential energy surface and classical trajectory analysisThe effects of binding of CO 2 or H 2 O with 9-hydroxyphenalenone ͑9HPO͒ on proton tunneling in the S 0 state have been theoretically investigated. High-level ab initio calculations predict that CO 2 is van der Waals-bonded to the CvO¯OH moiety of 9HPO in the most stable structure. This planar structure is more stable than the nonplanar structure where CO 2 is bonded above the aromatic rings of 9HPO. In the 9HPO-H 2 O complex, H 2 O is hydrogen-bonded to the carbonyl group in the most stable structure. Two-dimensional potential energy surfaces ͑PESs͒ for 9HPO-CO 2 and 9HPO-H 2 O have been calculated with the reaction surface method, and the contour plots of PESs for the complexes are compared with those for the 9HPO monomer. The binding of CO 2 with 9HPO induces slight asymmetry in the double-minimum potential well, whereas the asymmetry of the PES is very large for the binding of H 2 O. The transition state energy for 9HPO-CO 2 drastically decreases to be about a half that of 9HPO, while that for 9HPO-H 2 O is only slightly smaller than the transition energy for 9HPO. The vibrational wave function for in 9HPO-CO 2 is substantially delocalized over two potential minima, but that for 9HPO-H 2 O is completely localized around a single potential minimum. The calculated tunneling splitting of the zero-point level in 9HPO-CO 2 is only 10% smaller than the corresponding splitting of 9HPO, whereas proton tunneling is quenched in 9HPO-H 2 O. The calculated results are consistent with the prediction from the electronic spectra measured in a supersonic free jet.

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Cited by 16 publications

References 30 publications

Tunneling dynamics of internal rotation in the nitric acid molecule

Tunneling dynamics of internal rotation in the nitric acid molecule

Time-resolved photoelectron spectroscopy of proton transfer in the ground state of chloromalonaldehyde: Wave-packet dynamics on effective potential surfaces of reduced dimensionality

Effects of intermolecular interaction on proton tunneling: Theoretical study on two-dimensional potential energy surfaces for 9-hydroxyphenalenone-CO2/H2O complexes

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