Title: Electronic spectrum and characterization of diabatic potential energy surfaces for thiophenol

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/c8cp05215h · OSTI ID:1611114
ORCiD logo [1]; ORCiD logo [2];  [3]
  1. Harbin Institute of Technology (China); Univ. of Minnesota, Minneapolis, MN (United States); DOE/OSTI
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Harbin Institute of Technology (China)
+ Show Author Affiliations

The electronic spectrum of thiophenol was simulated by a normal-mode sampling approach combined with TDDFT in the Tamm–Dancoff approximation (TDA). The vertical excitation energies were compared with electronic structure calculations by completely renormalized equation-of-motion coupled cluster theory with single and double excitations and noniterative inclusion of connected triples (CR-EOM-CCSD(T)) and by multi-reference perturbation theory. The spectrum was computed both with and without solvation effects, and these spectra are compared to each other and to experiment. Using multireference-perturbation-theory adiabatic wave functions and model-space diabatization by the fourfold way, diabatic potential energy surfaces of the lowest three singlet states (1ππ, 1ππ*, and 1nπσ*) were constructed along the S–H stretching coordinate, the C–C–S–H torsion coordinate, and the v16a and v16b normal coordinates. The first two of these two are primary coordinates for the photodissociation, and the diabatic crossing seams of the three states were calculated and plotted as functions of the two coordinates. The other two coordinates are out-of-plane ring distortion modes studied to assess the extent of their role in coupling the states near the first conical intersection, and the v16a mode was shown to be an important coupling mode there. The current study is the first step toward a detailed mechanistic analysis of the photoinduced S–H fission process of thiophenol, a test system to understand 1nπσ*-mediated reactions, at the same time already providing a better understanding of the thiophenol electronic excitations by clarifying the assignment of the experimental results.

Research Organization:
University of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0008666; SC0015997
OSTI ID:
1611114
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 44 Vol. 20; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (83)

Zur Quantentheorie der Molekeln journal January 1927
Intramolecular Orbital Alignment Observed in the Photodissociation of [D1]Thiophenol journal September 2006
Control of Intramolecular Orbital Alignment in the Photodissociation of Thiophenol: Conformational Manipulation by Chemical Substitution journal February 2008
Factors Affecting the Branching Ratio of Photodissociation: Thiophenol Studied through Quantum Wavepacket Dynamics journal March 2015
Intruder state avoidance multireference Møller-Plesset perturbation theory: Multireference Møller-Plesset Perturbation Theory journal May 2002
Multiwfn: A multifunctional wavefunction analyzer journal December 2011
Interaction potentials and dynamics for Li + F collisions journal January 1974
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal July 2007
Determination of diabatic states through enforcement of configurational uniformity
  • Atchity, Gregory J.; Ruedenberg, Klaus
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4 https://doi.org/10.1007/s002140050236
journal October 1997
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr journal May 1989
MCSCF reference quasidegenerate perturbation theory with Epstein—Nesbet partitioning journal May 1993
Time-dependent density functional theory within the Tamm–Dancoff approximation journal December 1999
Ab initio investigations on the photophysics of indole journal December 1999
Conical intersections induced by repulsive 1πσ* states in planar organic molecules: malonaldehyde, pyrrole and chlorobenzene as photochemical model systems journal September 2000
Properties of nonadiabatic couplings and the generalized Born–Oppenheimer approximation journal March 2002
Study of proton-coupled electron transfer (PCET) with four explicit diabatic states at the ab initio level journal September 2017
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
Direct diabatization of electronic states by the fourfold-way: Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals journal June 2013
Theoretical study of the extremely small torsional barriers of thiophenol in the ground and the first excited electronic states journal August 2013
On the ultrashort lifetime of electronically excited thiophenol journal September 2016
Three-Dimensional Diabatic Potential Energy Surfaces for the Photodissociation of Thiophenol journal October 2017
Nonadiabatic Effect in Photodissociation Dynamics of Thiophenol via the 1 ππ* State journal June 2018
(ππ*/πσ*) Conical Intersection Seam Experimentally Observed in the S–D Bond Dissociation Reaction of Thiophenol- d 1 journal July 2015
Nonintuitive Diabatic Potential Energy Surfaces for Thioanisole journal August 2015
Insights for an Accurate Comparison of Computational Data to Experimental Absorption and Emission Spectra: Beyond the Vertical Transition Approximation journal March 2013
Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol journal July 2013
Anchor Points Reactive Potential for Bond-Breaking Reactions journal February 2014
Mixing of ionic and covalent configurations for sodium hydride, potassium hydride, and hydromagnesium(1+). Potential energy curves and couplings between molecular states journal December 1975
The Crossing of Potential Surfaces. journal January 1937
Photoinduced Electron and Proton Transfer in Phenol and Its Clusters with Water and Ammonia † journal October 2001
Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory journal March 2003
Controlling Electronic Product Branching at Conical Intersections in the UV Photolysis of para -Substituted Thiophenols journal November 2012
Near-Ultraviolet Photodissociation of Thiophenol † journal October 2008
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Photodissociation Dynamics of Thiophenol- d 1 : The Nature of Excited Electronic States along the S−D Bond Dissociation Coordinate journal October 2009
Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method:  Theoretical Bases, Computational Implementation, and Numerical Applications journal December 1997
πσ* excited states in molecular photochemistry journal January 2010
Full-dimensional potentials and state couplings and multidimensional tunneling calculations for the photodissociation of phenol journal January 2014
Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole journal January 2015
MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions journal January 2016
Excited-state hydrogen detachment and hydrogen transfer driven by repulsive 1πσ* states: A new paradigm for nonradiative decay in aromatic biomolecules journal February 2002
Linking photochemistry in the gas and solution phase: S–H bond fission in p-methylthiophenol following UV photoexcitation journal January 2011
Contrasting the excited state reaction pathways of phenol and para-methylthiophenol in the gas and liquid phases journal January 2012
The role of πσ* states in the photochemistry of heteroaromatic biomolecules and their subunits: insights from gas-phase femtosecond spectroscopy journal January 2014
Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited journal June 2001
Construction scheme for regularized diabatic states journal August 2001
The direct calculation of diabatic states based on configurational uniformity journal January 2001
New exchange-correlation density functionals: The role of the kinetic-energy density journal June 2002
Direct diabatization of electronic states by the fourfold way. II. Dynamical correlation and rearrangement processes journal September 2002
Extension of the fourfold way for calculation of global diabatic potential energy surfaces of complex, multiarrangement, non-Born–Oppenheimer systems: Application to HNCO(S0,S1) journal April 2003
New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states journal January 2004
Theoretical study of curve crossing: ab initio calculations on the four lowest 1 Σ + states of LiF journal November 1974
Many‐Electron Theory of Nonclosed‐Shell Atoms and Molecules. I. Orbital Wavefunction and Perturbation Theory journal March 1966
Formation and relaxation of excited states in solution: A new time dependent polarizable continuum model based on time dependent density functional theory journal March 2006
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions journal November 2006
Experimental and theoretical study of the photodissociation reaction of thiophenol at 243nm: Intramolecular orbital alignment of the phenylthiyl radical journal January 2007
Nested variant of the method of moments of coupled cluster equations for vertical excitation energies and excited-state potential energy surfaces journal May 2009
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory journal June 2011
A quadratically convergent MCSCF method for the simultaneous optimization of several states journal May 1981
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Coupled cluster response functions journal September 1990
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon journal January 1993
The equation of motion coupled‐cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties journal May 1993
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Quasidegenerate perturbation theory with multiconfigurational self‐consistent‐field reference functions journal November 1993
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr journal April 1994
Theoretical analysis of photoinduced H-atom elimination in thiophenol journal May 2012
A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics journal August 1997
Model space diabatization for quantum photochemistry journal February 2015
The near ultraviolet photodissociation dynamics of 2- and 3-substituted thiophenols: Geometric vs. electronic structure effects journal July 2017
Exploring nuclear motion through conical intersections in the UV photodissociation of phenols and thiophenol journal July 2008
The concept of regularized diabatic states for a general conical intersection journal March 2006
A 'quasi-diabatic' representation for inelastic collisions Application to the scattering of He + by Ne journal August 1971
Resonant Charge Exchange in Atomic Collisions journal July 1963
The Normal Modes and Frequencies of Vibration of the Regular Plane Hexagon Model of the Benzene Molecule journal May 1934
Non-Adiabatic Meson Theory of Nuclear Forces journal May 1950
Molecular study of the H + -Kr collisional system journal July 1976
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Quantum-Mechanical Calculation of Cross Sections for Inelastic Atom-Atom Collisions. I. Inelastic 2 S 3 → 2 P 3 Collisions between Metastable and Ground-State Helium Atoms journal December 1971
Relative likelihood of encountering conical intersections and avoided intersections on the potential energy surfaces of polyatomic molecules journal September 2003
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
The Diabatic Picture of Electron Transfer, Reaction Barriers, and Molecular Dynamics journal March 2010
The Construction and Interpretation of Mcscf Wavefunctions journal October 1998

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