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The predicted value of potential barrier to internal rotation of benzaldehyde: Is there a conflict between the theory and the experiment or not?

Igor Andreevich Godunov ¹

Igor Andreevich Godunov

,

Gul'nara Maratovna Kuramshina ¹

Gul'nara Maratovna Kuramshina

Orcid

0000-0002-4044-471X

¹ Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow, Russian Federation

10.1016/j.mencom.2023.06.044

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Published 2023-06-13

Communication , Volume 33, Issue 4, 577-581

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Godunov I. A., Kuramshina G. M. The predicted value of potential barrier to internal rotation of benzaldehyde: Is there a conflict between the theory and the experiment or not? // Mendeleev Communications. 2023. Vol. 33. No. 4. pp. 577-581.

GOST all authors (up to 50) Copy

Godunov I. A., Kuramshina G. M. The predicted value of potential barrier to internal rotation of benzaldehyde: Is there a conflict between the theory and the experiment or not? // Mendeleev Communications. 2023. Vol. 33. No. 4. pp. 577-581.

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TY - JOUR

DO - 10.1016/j.mencom.2023.06.044

UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.06.044

TI - The predicted value of potential barrier to internal rotation of benzaldehyde: Is there a conflict between the theory and the experiment or not?

T2 - Mendeleev Communications

AU - Godunov, Igor Andreevich

AU - Kuramshina, Gul'nara Maratovna

PY - 2023

DA - 2023/06/13

PB - Mendeleev Communications

SP - 577-581

IS - 4

VL - 33

ER -

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@article{2023_Godunov,

author = {Igor Andreevich Godunov and Gul'nara Maratovna Kuramshina},

title = {The predicted value of potential barrier to internal rotation of benzaldehyde: Is there a conflict between the theory and the experiment or not?},

journal = {Mendeleev Communications},

year = {2023},

volume = {33},

publisher = {Mendeleev Communications},

month = {Jun},

url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.06.044},

number = {4},

pages = {577--581},

doi = {10.1016/j.mencom.2023.06.044}

}

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Godunov, Igor Andreevich, and Gul'nara Maratovna Kuramshina. “The predicted value of potential barrier to internal rotation of benzaldehyde: Is there a conflict between the theory and the experiment or not?.” Mendeleev Communications, vol. 33, no. 4, Jun. 2023, pp. 577-581. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.06.044.

Keywords

benzaldehyde

experimental torsion energy levels

matrix elements of vibration kinetic energy.

potential barrier to internal rotation

quantum chemical calculations

two-dimensional model

Abstract

The ratio of potential barrier heights for the internal rotation of benzaldehyde molecule calculated by quantum mechanical methods and determined experimentally from UV spectra has been discussed. Based on the joint analysis of the results of ab initio MP2/6-311G** calculations of normal vibrations of benzaldehyde in the ground state and the results of interpretation of the observed UV spectra of the compound, possible approximations for a correct description of the hindered internal rotation of the aldehyde group have been considered. The two-dimensional model including the kinematic interaction between torsion and out-of-plane deformation of aldehyde group has been established as more efficient for the correct description of the hindered rotation in benzaldehyde.

References

.

The Barriers to Internal Rotation of Benzaldehyde and Benzoyl Fluoride: “Reconciliation” Between Theory and Experiment

10.1021/jp509602s

The Barriers to Internal Rotation of Benzaldehyde and Benzoyl Fluoride: “Reconciliation” Between Theory and Experiment

Godunov I.A., Bataev V.A., Abramenkov A.V., Pupyshev V.I.

Journal of Physical Chemistry A, 2014

.

Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes

10.1016/j.saa.2016.02.029

Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes

Bataev V.A., Pupyshev V.I., Godunov I.A.

Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2016

.

An alternative calculation of the vibrational potential energy distribution

10.1016/0022-2860(71)87090-4

An alternative calculation of the vibrational potential energy distribution

Keresztury G., Jalsovszky G.

Journal of Molecular Structure, 1971

.

Far infrared spectra and barriers to internal rotation of benzaldehyde, benzoyl fluoride, benzoyl chloride and acetophenone

10.1016/0022-2860(85)80191-5

Far infrared spectra and barriers to internal rotation of benzaldehyde, benzoyl fluoride, benzoyl chloride and acetophenone

Durig J.R., Bist H.D., Furic K., Qiu J., Little T.S.

Journal of Molecular Structure, 1985

.

Joint treatment of ab initio and experimental data in molecular force field calculations with Tikhonov’s method of regularization

10.1063/1.466619

Joint treatment of ab initio and experimental data in molecular force field calculations with Tikhonov’s method of regularization

Kuramshina G.M., Weinhold F., Kochikov I.V., Yagola A.G., Pentin Y.A.

Journal of Chemical Physics, 1994

.

Quantum-mechanical studies on the origin of barriers to internal rotation about single bonds

10.1021/ja00501a009

Quantum-mechanical studies on the origin of barriers to internal rotation about single bonds

Brunck T.K., Weinhold F.

Journal of the American Chemical Society, 1979

.

Ab Initio Study of the Torsional Spectrum of Glycolaldehyde

10.1021/jp0489121

Ab Initio Study of the Torsional Spectrum of Glycolaldehyde

Senent M.L.

Journal of Physical Chemistry A, 2004

.

$Molecular Geometry of Benzaldehyde and Salicylaldehyde: A Gas-Phase Electron Diffraction and ab Initio Molecular Orbital Investigation$

10.1021/jp953629a

Molecular Geometry of Benzaldehyde and Salicylaldehyde: A Gas-Phase Electron Diffraction and ab Initio Molecular Orbital Investigation

Borisenko K.B., Bock C.W., Hargittai I.

The Journal of Physical Chemistry, 1996

.

Physics behind the Barrier to Internal Rotation of an Acetyl Chloride Molecule: A Combined Approach from Density Functional Theory, Car–Parrinello Molecular Dynamics, and Time-Resolved Wavelet Transform Theory

10.1021/acsomega.8b00316

Physics behind the Barrier to Internal Rotation of an Acetyl Chloride Molecule: A Combined Approach from Density Functional Theory, Car–Parrinello Molecular Dynamics, and Time-Resolved Wavelet Transform Theory

Dutta B., Bhattacharjee B., Chowdhury J.

ACS Omega, 2018

.

The rotational spectra, electric dipole moments and molecular structures of anisole and benzaldehyde

10.1039/b501041a

The rotational spectra, electric dipole moments and molecular structures of anisole and benzaldehyde

Desyatnyk O., Pszczółkowski L., Thorwirth S., Krygowski T.M., Kisiel Z.

Physical Chemistry Chemical Physics, 2005

.

High-resolution FTIR spectroscopy of benzaldehyde in the far-infrared region: probing the rotational barrier

10.1039/d1cp00188d

High-resolution FTIR spectroscopy of benzaldehyde in the far-infrared region: probing the rotational barrier

Liang Y., Zhang Y., Fábri C., Ma J., Zhao J., Billinghurst B., Chen Z.

Physical Chemistry Chemical Physics, 2021

.

Reply to comment on "Internal rotation in conjugated molecules: substituted ethylenes and benzenes"

10.1021/j100141a057

Reply to comment on "Internal rotation in conjugated molecules: substituted ethylenes and benzenes"

Head-Gordon M., Pople J.A.

The Journal of Physical Chemistry, 1993

.

Comment on "Internal rotation in conjugated molecules: substituted ethylenes and benzenes"

10.1021/j100141a056

Comment on "Internal rotation in conjugated molecules: substituted ethylenes and benzenes"

Meier R.J.

The Journal of Physical Chemistry, 1993

.

The 1-D hindered rotor approximation

10.1007/s00214-007-0376-5

The 1-D hindered rotor approximation

Pfaendtner J., Yu X., Broadbelt L.J.

Theoretical Chemistry Accounts, 2007

.

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation: II. Unsymmetrical Tops Attached to a Rigid Frame

10.1063/1.1932193

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation: II. Unsymmetrical Tops Attached to a Rigid Frame

Pitzer K.S.

Journal of Chemical Physics, 1946

.

Conformations and rotational barriers of aromatic polyesters

10.1016/0166-1280(92)87023-S

Conformations and rotational barriers of aromatic polyesters

Coussensa B., Pierloot K., Meier R.J.

Journal of Molecular Structure THEOCHEM, 1992

.

Vibration‐Hindered Rotation Interactions in Methyl Alcohol. The J=0→1 Transition

10.1063/1.1743263

Vibration‐Hindered Rotation Interactions in Methyl Alcohol. The J=0→1 Transition

Hecht K.T., Dennison D.M.

Journal of Chemical Physics, 1957

.

UNDERSTANDING BARRIERS TO INTERNAL ROTATION IN SUBSTITUTED TOLUENES

10.1063/1.469151

UNDERSTANDING BARRIERS TO INTERNAL ROTATION IN SUBSTITUTED TOLUENES

Lu K., Weinhold F., Weisshaar J.C.

Journal of Chemical Physics, 1995

.

An ab initio structural and spectroscopic study of acetone—An analysis of the far infrared torsional spectra of acetone‐h6 and ‐d6

10.1063/1.464157

An ab initio structural and spectroscopic study of acetone—An analysis of the far infrared torsional spectra of acetone‐h6 and ‐d6

Smeyers Y.G., Senent M.L., Botella V., Moule D.C.

Journal of Chemical Physics, 1993

.

Vibrational spectra of benzene derivatives—XVI. Benzaldehyde and mono-substituted benzaldehydes

10.1016/0584-8539(76)80165-1

Vibrational spectra of benzene derivatives—XVI. Benzaldehyde and mono-substituted benzaldehydes

Green J.H., Harrison D.J.

Spectrochimica Acta Part A Molecular Spectroscopy, 1976

.

Ab initiodetermination of the far infrared spectra of some isotopic varieties of ethanol

10.1063/1.481155

Ab initiodetermination of the far infrared spectra of some isotopic varieties of ethanol

Senent M.L., Smeyers Y.G., Domı́nguez-Gómez R., Villa M.

Journal of Chemical Physics, 2000

.

Ab initiodetermination of the torsional spectra of acetic acid

10.1080/00268970110048374

Ab initiodetermination of the torsional spectra of acetic acid

SENENT M.L.

Molecular Physics, 2001

.

Changes in the phase of the barrier to internal rotation upon electronic excitation

10.1080/01442358609353372

Changes in the phase of the barrier to internal rotation upon electronic excitation

Gordon R.D.

International Reviews in Physical Chemistry, 1986

.

Investigation of torsional potentials, hindered rotation, molecular structure and vibrational properties of some biphenyl carboxaldehydes using spectroscopic techniques and density functional formalism

10.1016/j.molstruc.2019.06.064

Investigation of torsional potentials, hindered rotation, molecular structure and vibrational properties of some biphenyl carboxaldehydes using spectroscopic techniques and density functional formalism

Srishailam K., Reddy B.V., Rao G.R.

Journal of Molecular Structure, 2019

.

The microwave and infrared spectroscopy of benzaldehyde: Conflict between theory and experimental deductions

10.1063/1.1643716

The microwave and infrared spectroscopy of benzaldehyde: Conflict between theory and experimental deductions

Speakman L.D., Papas B.N., Woodcock H.L., Schaefer H.F.

Journal of Chemical Physics, 2004

.

On the problem of theoretical evaluation of the rotational barrier in aromatics with adjacent conjugated group: benzaldehyde and N-methylbenzamide

10.1016/S0009-2614(02)00032-5

On the problem of theoretical evaluation of the rotational barrier in aromatics with adjacent conjugated group: benzaldehyde and N-methylbenzamide

Meier R.J., Koglin E.

Chemical Physics Letters, 2002

.

A Theoretical Study of the Methyl and Aldehyde Torsion FIR Spectra in Symmetric Propanal Isotopomers

10.1006/jmsp.2000.8068

A Theoretical Study of the Methyl and Aldehyde Torsion FIR Spectra in Symmetric Propanal Isotopomers

Smeyers Y.G., Villa M., Uc V.H., Vivier-Bunge A.

Journal of Molecular Spectroscopy, 2000