An improved quasi-diabatic representation of the 1, 2, 31 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates
Abstract
In a previous project we constructed a quasi-diabatic representation, Hd, of the 1, 2, 31A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That Hd accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of Hd for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accurate Hd compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data indicate an alternative interpretation of kinetic energy release measurements near λphot ~ 248 nm.
- Authors:
-
- Johns Hopkins Univ., Baltimore, MD (United States)
- Publication Date:
- Research Org.:
- Johns Hopkins Univ., Baltimore, MD (United States); University of California, Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1599341
- Alternate Identifier(s):
- OSTI ID: 1421161
- Grant/Contract Number:
- FG02-91ER14189; AC02-5CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 12; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhu, Xiaolei, Malbon, Christopher L., and Yarkony, David R. An improved quasi-diabatic representation of the 1, 2, 31 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates. United States: N. p., 2016.
Web. doi:10.1063/1.4944091.
Zhu, Xiaolei, Malbon, Christopher L., & Yarkony, David R. An improved quasi-diabatic representation of the 1, 2, 31 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates. United States. https://doi.org/10.1063/1.4944091
Zhu, Xiaolei, Malbon, Christopher L., and Yarkony, David R. Thu .
"An improved quasi-diabatic representation of the 1, 2, 31 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates". United States. https://doi.org/10.1063/1.4944091. https://www.osti.gov/servlets/purl/1599341.
@article{osti_1599341,
title = {An improved quasi-diabatic representation of the 1, 2, 31 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates},
author = {Zhu, Xiaolei and Malbon, Christopher L. and Yarkony, David R.},
abstractNote = {In a previous project we constructed a quasi-diabatic representation, Hd, of the 1, 2, 31A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That Hd accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of Hd for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accurate Hd compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data indicate an alternative interpretation of kinetic energy release measurements near λphot ~ 248 nm.},
doi = {10.1063/1.4944091},
journal = {Journal of Chemical Physics},
number = 12,
volume = 144,
place = {United States},
year = {Thu Mar 31 00:00:00 EDT 2016},
month = {Thu Mar 31 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Exploring nuclear motion through conical intersections in the UV photodissociation of phenols and thiophenol
journal, July 2008
- Ashfold, M. N. R.; Devine, A. L.; Dixon, R. N.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 35
Ultraviolet photoelectron spectroscopy of the phenide, benzyl and phenoxide anions, with ab initio calculations
journal, September 1992
- Gunion, Robert F.; Gilles, Mary K.; Polak, Mark L.
- International Journal of Mass Spectrometry and Ion Processes, Vol. 117
The 2750-Å electronic band system of phenol
journal, January 1966
- Bist, H. D.; Brand, J. C. D.; Williams, D. R.
- Journal of Molecular Spectroscopy, Vol. 21, Issue 1-4
Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol
journal, July 2013
- Xu, Xuefei; Yang, Ke R.; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 9, Issue 8
Nuclear dynamics near conical intersections in the adiabatic representation: I. The effects of local topography on interstate transitions
journal, February 2001
- Yarkony, David R.
- The Journal of Chemical Physics, Vol. 114, Issue 6
On the elimination of the electronic structure bottleneck in on the fly nonadiabatic dynamics for small to moderate sized (10-15 atom) molecules using fit diabatic representations based solely on ab initio electronic structure data: The photodissociation of phenol
journal, January 2016
- Zhu, Xiaolei; Yarkony, David R.
- The Journal of Chemical Physics, Vol. 144, Issue 2
Conformationally selective photodissociation dynamics of propanal cation
journal, February 2011
- Tao, Hongli; Shen, Lei; Kim, Myung Hwa
- The Journal of Chemical Physics, Vol. 134, Issue 5
The S 1 state geometry of phenol determined by simultaneous Franck–Condon and rotational constants fits
journal, January 2003
- Spangenberg, Daniel; Imhof, Petra; Kleinermanns, Karl
- Phys. Chem. Chem. Phys., Vol. 5, Issue 12
Microwave spectra of the six mono-13C-substituted phenols and of some monodeuterated species of phenol. Complete substitution structure and absolute dipole moment
journal, January 1979
- Larsen, N. W.
- Journal of Molecular Structure, Vol. 51
The 2750-Å band system of phenol
journal, January 1967
- Bist, H. D.; Brand, J. C. D.; Williams, D. R.
- Journal of Molecular Spectroscopy, Vol. 24, Issue 1-4
A multi-sheeted three-dimensional potential-energy surface for the H-atom photodissociation of phenol
journal, January 2013
- Ramesh, Sai G.; Domcke, Wolfgang
- Faraday Discussions, Vol. 163
Fitting coupled potential energy surfaces for large systems: Method and construction of a 3-state representation for phenol photodissociation in the full 33 internal degrees of freedom using multireference configuration interaction determined data
journal, January 2014
- Zhu, Xiaolei; Yarkony, David R.
- The Journal of Chemical Physics, Vol. 140, Issue 2
Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols
journal, January 2014
- Karsili, Tolga N. V.; Wenge, Andreas M.; Marchetti, Barbara
- Phys. Chem. Chem. Phys., Vol. 16, Issue 2
Photodissociation Dynamics of Diacetylene Rydberg States
journal, November 2015
- Wang, Hongzhen; Yu, Shengrui; Su, Shu
- The Journal of Physical Chemistry A, Vol. 119, Issue 46
Theoretical Investigation of Molecular Properties of the First Excited State of the Phenoxyl Radical
journal, March 2008
- Cheng, Chi-Wen; Lee, Yuan-Pern; Witek, Henryk A.
- The Journal of Physical Chemistry A, Vol. 112, Issue 12
O–H bond fission in 4-substituted phenols: S1 state predissociation viewed in a Hammett-like framework
journal, January 2013
- Karsili, Tolga N. V.; Wenge, Andreas M.; Harris, Stephanie J.
- Chemical Science, Vol. 4, Issue 6
Ab initio characterization of the conical intersections involved in the photochemistry of phenol
journal, December 2008
- Vieuxmaire, Olivier P. J.; Lan, Zhenggang; Sobolewski, Andrzej L.
- The Journal of Chemical Physics, Vol. 129, Issue 22
Exploring the Time-Scales of H-Atom Detachment from Photoexcited Phenol- h 6 and Phenol- d 5 : Statistical vs Nonstatistical Decay
journal, July 2009
- Iqbal, Azhar; Cheung, Michelle S. Y.; Nix, Michael G. D.
- The Journal of Physical Chemistry A, Vol. 113, Issue 29
Dynamics at conical intersections: The influence of O–H stretching vibrations on the photodissociation of phenol
journal, March 2008
- Hause, Michael L.; Heidi Yoon, Y.; Case, Amanda S.
- The Journal of Chemical Physics, Vol. 128, Issue 10
A CASPT2 study of the valence and lowest Rydberg electronic states of benzene and phenol
journal, April 1995
- Lorentzon, Johan; Malmqvist, Per-�ke; F�lscher, Markus
- Theoretica Chimica Acta, Vol. 91, Issue 1-2
Direct Observation of Hydrogen Tunneling Dynamics in Photoexcited Phenol
journal, January 2012
- Roberts, Gareth M.; Chatterley, Adam S.; Young, Jamie D.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 3
Excited state hydrogen transfer dynamics in substituted phenols and their complexes with ammonia: ππ∗-πσ∗ energy gap propensity and ortho -substitution effect
journal, September 2010
- Pino, G. A.; Oldani, A. N.; Marceca, E.
- The Journal of Chemical Physics, Vol. 133, Issue 12
Tunnelling under a conical intersection: Application to the product vibrational state distributions in the UV photodissociation of phenols
journal, May 2011
- Dixon, Richard N.; Oliver, Thomas A. A.; Ashfold, Michael N. R.
- The Journal of Chemical Physics, Vol. 134, Issue 19
Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol
journal, June 2005
- Lan, Zhenggang; Domcke, Wolfgang; Vallet, Valérie
- The Journal of Chemical Physics, Vol. 122, Issue 22
Near-UV photolysis of substituted phenols : Part II. 4-, 3- and 2-methylphenol
journal, January 2008
- King, Graeme A.; Devine, Adam L.; Nix, Michael G. D.
- Physical Chemistry Chemical Physics, Vol. 10, Issue 42
Observation of geometric phase effect induced photodissociation dynamics in phenol
journal, October 2008
- Nix, M. G. D.; Devine, A. L.; Dixon, R. N.
- Chemical Physics Letters, Vol. 463, Issue 4-6
Photodissociation dynamics of the methyl perthiyl radical at 248 nm via photofragment translational spectroscopy
journal, February 2013
- Cole-Filipiak, Neil C.; Negru, Bogdan; Just, Gabriel M. P.
- The Journal of Chemical Physics, Vol. 138, Issue 5
High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of phenol
journal, October 2006
- Nix, Michael G. D.; Devine, Adam L.; Cronin, Bríd
- The Journal of Chemical Physics, Vol. 125, Issue 13
Near-Ultraviolet Photodissociation of Thiophenol †
journal, October 2008
- Devine, Adam L.; Nix, Michael G. D.; Dixon, Richard N.
- The Journal of Physical Chemistry A, Vol. 112, Issue 39
Molecular dynamics with electronic transitions
journal, July 1990
- Tully, John C.
- The Journal of Chemical Physics, Vol. 93, Issue 2
The vibrational spectrum and torsion of phenol
journal, January 1967
- Bist, H. D.; Brand, J. C. D.; Williams, D. R.
- Journal of Molecular Spectroscopy, Vol. 24, Issue 1-4
Conical Intersections: Diabolical and Often Misunderstood
journal, August 1998
- Yarkony, David R.
- Accounts of Chemical Research, Vol. 31, Issue 8
The symmetry groups of non-rigid molecules
journal, January 2002
- Longuet-Higgins, H. C.
- Molecular Physics, Vol. 100, Issue 1
The symmetry groups of non-rigid molecules
journal, June 1963
- Longuet-Higgins, H. C.
- Molecular Physics, Vol. 6, Issue 5
Benzyl Radical Photodissociation Dynamics at 248 nm
journal, September 2015
- Shapero, Mark; Cole-Filipiak, Neil C.; Haibach-Morris, Courtney
- The Journal of Physical Chemistry A, Vol. 119, Issue 50
Microwave spectra of the six mono-13C-substituted phenols and of some monodeuterated species of phenol. Complete substitution structure and absolute dipole moment.
journal, November 1985
- Larsem, N. W.
- Journal of Molecular Structure, Vol. 131, Issue 3-4, p. 398
A CASPT2 study of the valence and lowest Rydberg electronic states of benzene and phenol
journal, January 1995
- Lorentzon, Johan; Malmqvist, Per-A˚ke; Fülscher, Markus
- Theoretica Chimica Acta, Vol. 91, Issue 1
Works referencing / citing this record:
Diabatic Hamiltonian construction in van der Waals heterostructure complexes
journal, January 2019
- Xie, Yu; Sun, Huijuan; Zheng, Qijing
- Journal of Materials Chemistry A, Vol. 7, Issue 48
Excited-state dissociation dynamics of phenol studied by a new time-resolved technique
journal, February 2018
- Lin, Yen-Cheng; Lee, Chin; Lee, Shih-Huang
- The Journal of Chemical Physics, Vol. 148, Issue 7
Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects
journal, September 2018
- He, Ying; Zhao, Huali; Wang, Wenji
- International Journal of Quantum Chemistry, Vol. 118, Issue 24
Accuracy of trajectory surface-hopping methods: Test for a two-dimensional model of the photodissociation of phenol
journal, November 2017
- Xie, Weiwei; Domcke, Wolfgang
- The Journal of Chemical Physics, Vol. 147, Issue 18
Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH 2 OH photodissociation
journal, April 2017
- Malbon, Christopher L.; Yarkony, David R.
- The Journal of Chemical Physics, Vol. 146, Issue 13
Diabatic Hamiltonian Construction in van der Waals heterostructure complexes
preprint, January 2019
- Xie, Yu; Sun, Huijuan; Zheng, Qijing
- arXiv