Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol

Xie, Changjian; Zhao, Bin; Malbon, Christopher L.; Yarkony, David R.; Xie, Daiqian; Guo, Hua

doi:10.1021/acs.jpclett.9b03407

Title: Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol

Abstract

The fate of a photoexcited molecule is often strongly influencedby electronic degeneracies, such as conical intersections, which break the Born-Oppenheimer separation of electronic and nuclear motion. Detailed information concerning internal energy redistribution in a nonadiabatic process can beextracted from the product state distribution of a photofragment in photo-dissociation. Here, we focus on the nonadiabatic photodissociation of phenol and discuss the internal excitation of the phenoxyl fragment using both symmetry analysis and wave packet dynamics. It is shown that unique and general selection rules exist, which can be attributed to the geometric phase in the adiabatic representation. Further, our results provide a reinterpretation of the experimental data, shedding light on the importance of conical intersections on the product state distribution.

Authors:

Xie, Changjian ^[1];

^[2]; Malbon, Christopher L. ^[3];

^[3];

^[4];

^[2]

Univ. of New Mexico, Albuquerque, NM (United States); Northwest Univ., Shaanxi (China)
Univ. of New Mexico, Albuquerque, NM (United States)
Johns Hopkins Univ., Baltimore, MD (United States)
Nanjing Univ. (China)

Publication Date:: Tue Dec 10 00:00:00 EST 2019

Research Org.:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1596358

Grant/Contract Number:: SC0015997

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Xie, Changjian, Zhao, Bin, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, and Guo, Hua. Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpclett.9b03407.

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                    Xie, Changjian, Zhao, Bin, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, & Guo, Hua. Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol.  United States.  https://doi.org/10.1021/acs.jpclett.9b03407

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                    Xie, Changjian, Zhao, Bin, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, and Guo, Hua. Tue .  
"Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol".  United States.  https://doi.org/10.1021/acs.jpclett.9b03407.  https://www.osti.gov/servlets/purl/1596358.

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@article{osti_1596358,

  title        = {Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol},

  author       = {Xie, Changjian and Zhao, Bin and Malbon, Christopher L. and Yarkony, David R. and Xie, Daiqian and Guo, Hua},

  abstractNote = {The fate of a photoexcited molecule is often strongly influencedby electronic degeneracies, such as conical intersections, which break the Born-Oppenheimer separation of electronic and nuclear motion. Detailed information concerning internal energy redistribution in a nonadiabatic process can beextracted from the product state distribution of a photofragment in photo-dissociation. Here, we focus on the nonadiabatic photodissociation of phenol and discuss the internal excitation of the phenoxyl fragment using both symmetry analysis and wave packet dynamics. It is shown that unique and general selection rules exist, which can be attributed to the geometric phase in the adiabatic representation. Further, our results provide a reinterpretation of the experimental data, shedding light on the importance of conical intersections on the product state distribution.},

  doi          = {10.1021/acs.jpclett.9b03407},

  journal      = {Journal of Physical Chemistry Letters},

  number       = 1,

  volume       = 11,

  place        = {United States},

  year         = {Tue Dec 10 00:00:00 EST 2019},

  month        = {Tue Dec 10 00:00:00 EST 2019}

}

Copy to clipboard

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Title: Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol

Abstract

Citation Formats

Primary processes underlying the photostability of isolated DNA bases: Adenine journal, June 2006

Thymine Dimerization in DNA Is an Ultrafast Photoreaction journal, February 2007

Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases journal, November 2010

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Ab initio characterization of the conical intersections involved in the photochemistry of phenol journal, December 2008

Tunnelling under a conical intersection: Application to the product vibrational state distributions in the UV photodissociation of phenols journal, May 2011

Quantum Wave Packet Propagation Study of the Photochemistry of Phenol: Isotope Effects (Ph-OD) and the Direct Excitation to the 1 πσ* State journal, November 2011

A multi-sheeted three-dimensional potential-energy surface for the H-atom photodissociation of phenol journal, January 2013

Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol journal, July 2013

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

Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling journal, November 2014

An improved quasi-diabatic representation of the 1, 2, 3 1 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates journal, March 2016

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

Nonadiabatic Tunneling in Photodissociation of Phenol journal, June 2016

On the incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data journal, December 2016

Constructive and Destructive Interference in Nonadiabatic Tunneling via Conical Intersections journal, April 2017

Photodissociation of phenol via nonadiabatic tunneling: Comparison of two ab initio based potential energy surfaces journal, September 2017

Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems journal, July 2017

On the representation of coupled adiabatic potential energy surfaces using quasi-diabatic Hamiltonians: description of accidental seams of conical intersection journal, September 2010

Studies of the Jahn-Teller effect .II. The dynamical problem journal, February 1958

On the determination of Born–Oppenheimer nuclear motion wave functions including complications due to conical intersections and identical nuclei journal, March 1979

Geometric Phase Effects in Chemical Reaction Dynamics and Molecular Spectra journal, September 2003

Theoretical Study of Geometric Phase Effects in the Hydrogen-Exchange Reaction journal, August 2005

Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State journal, February 2018

Vibrations of the Phenoxyl Radical journal, November 2001

Rovibronic bands of the Ã B22←X̃ B21 transition of C6H5O and C6D5O detected with cavity ringdown absorption near 1.2 μm journal, October 2008

Theoretical Investigation of Molecular Properties of the First Excited State of the Phenoxyl Radical journal, March 2008

Absorption spectra of aromatic free radicals: a vibrational analysis of the 3050 Å absorption spectrum of benzyl and a new transition of phenoxyl journal, July 1968

Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2 2 A (3 s ) Rydberg state journal, January 2018

Primary processes underlying the photostability of isolated DNA bases: Adenine
journal, June 2006

Thymine Dimerization in DNA Is an Ultrafast Photoreaction
journal, February 2007

Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases
journal, November 2010

Ultrafast Excited-State Dynamics in Nucleic Acids
journal, April 2004

Nonadiabatic Events and Conical Intersections
journal, May 2011

Multimode Molecular Dynamics Beyond the Born-Oppenheimer Approximation
book, January 2007

Conical Intersections: Theory, Computation and Experiment
book, November 2011

Nonadiabatic Quantum Chemistry—Past, Present, and Future
journal, November 2011

Role of Conical Intersections in Molecular Spectroscopy and Photoinduced Chemical Dynamics
journal, May 2012

The Requisite Electronic Structure Theory To Describe Photoexcited Nonadiabatic Dynamics: Nonadiabatic Derivative Couplings and Diabatic Electronic Couplings
journal, May 2015

Up to a Sign. The Insidious Effects of Energetically Inaccessible Conical Intersections on Unimolecular Reactions
journal, January 2019

Photoinduced Electron and Proton Transfer in Phenol and Its Clusters with Water and Ammonia ^†
journal, October 2001

Excited-state hydrogen detachment and hydrogen transfer driven by repulsive 1πσ* states: A new paradigm for nonradiative decay in aromatic biomolecules
journal, February 2002

H atom elimination from the πσ∗ state in the photodissociation of phenol
journal, January 2004

The Role of * Excited States in the Photodissociation of Heteroaromatic Molecules
journal, June 2006

High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of phenol
journal, October 2006

Photodissociation Dynamics of Phenol ^†
journal, September 2007

Exploring nuclear motion through conical intersections in the UV photodissociation of phenols and thiophenol
journal, July 2008

Dynamics at conical intersections: The influence of O–H stretching vibrations on the photodissociation of phenol
journal, March 2008

Direct versus Indirect H Atom Elimination from Photoexcited Phenol Molecules
journal, October 2008

Observation of geometric phase effect induced photodissociation dynamics in phenol
journal, October 2008

Exploring the Time-Scales of H-Atom Detachment from Photoexcited Phenol- h ₆ and Phenol- d ₅ : Statistical vs Nonstatistical Decay
journal, July 2009

High Resolution Photofragment Translational Spectroscopy Studies of the Ultraviolet Photolysis of Phenol- d ₅
journal, July 2009

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

Direct Observation of Hydrogen Tunneling Dynamics in Photoexcited Phenol
journal, January 2012

Excited-state dissociation dynamics of phenol studied by a new time-resolved technique
journal, February 2018

Communication: Mode-dependent excited-state lifetime of phenol under the S ₁ /S ₂ conical intersection
journal, July 2018

Multidimensional H Atom Tunneling Dynamics of Phenol: Interplay between Vibrations and Tunneling
journal, February 2019

Near-UV photolysis of substituted phenols : Part II. 4-, 3- and 2-methylphenol
journal, January 2008

O–H bond fission in 4-substituted phenols: S1 state predissociation viewed in a Hammett-like framework
journal, January 2013

The near ultraviolet photodissociation dynamics of 2- and 3-substituted thiophenols: Geometric vs. electronic structure effects
journal, July 2017

Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol
journal, June 2005

Ab initio characterization of the conical intersections involved in the photochemistry of phenol
journal, December 2008

Tunnelling under a conical intersection: Application to the product vibrational state distributions in the UV photodissociation of phenols
journal, May 2011

Quantum Wave Packet Propagation Study of the Photochemistry of Phenol: Isotope Effects (Ph-OD) and the Direct Excitation to the ¹ πσ* State
journal, November 2011

A multi-sheeted three-dimensional potential-energy surface for the H-atom photodissociation of phenol
journal, January 2013

Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol
journal, July 2013

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

Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling
journal, November 2014

An improved quasi-diabatic representation of the 1, 2, 3 ¹ A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates
journal, March 2016

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

Nonadiabatic Tunneling in Photodissociation of Phenol
journal, June 2016

On the incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data
journal, December 2016

Constructive and Destructive Interference in Nonadiabatic Tunneling via Conical Intersections
journal, April 2017

Photodissociation of phenol via nonadiabatic tunneling: Comparison of two ab initio based potential energy surfaces
journal, September 2017

Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems
journal, July 2017

On the representation of coupled adiabatic potential energy surfaces using quasi-diabatic Hamiltonians: description of accidental seams of conical intersection
journal, September 2010

Studies of the Jahn-Teller effect .II. The dynamical problem
journal, February 1958

On the determination of Born–Oppenheimer nuclear motion wave functions including complications due to conical intersections and identical nuclei
journal, March 1979

Geometric Phase Effects in Chemical Reaction Dynamics and Molecular Spectra
journal, September 2003

Theoretical Study of Geometric Phase Effects in the Hydrogen-Exchange Reaction
journal, August 2005

Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State
journal, February 2018

Vibrations of the Phenoxyl Radical
journal, November 2001

Rovibronic bands of the Ã B22←X̃ B21 transition of C6H5O and C6D5O detected with cavity ringdown absorption near 1.2 μm
journal, October 2008

Theoretical Investigation of Molecular Properties of the First Excited State of the Phenoxyl Radical
journal, March 2008

Absorption spectra of aromatic free radicals: a vibrational analysis of the 3050 Å absorption spectrum of benzyl and a new transition of phenoxyl
journal, July 1968

Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2 ² A (3 s ) Rydberg state
journal, January 2018