Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Surface hopping investigation of the relaxation dynamics in radical cations

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.4939842 · OSTI ID:1435412
 [1];  [2];  [3]
  1. Temple Univ., Philadelphia, PA (United States); Univ. of Birmingham, Birmingham (United Kingdom); Temple University
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Temple Univ., Philadelphia, PA (United States)
+ Show Author Affiliations

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in these systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.

Research Organization:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-08ER15983
OSTI ID:
1435412
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 3 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (48)

Time-Resolved Photoelectron Spectroscopy of Nonadiabatic Dynamics in Polyatomic Molecules book March 2008
Femtosecond Time-Resolved Photoelectron Spectroscopy journal June 2004
The Ionization Potentials of Butadiene, Hexatriene, and their Methyl Derivatives: Evidence for through space interaction between double bond ?-orbitals and non-bonded pseudo-? orbitals of methyl groups? journal April 1973
Newton-X: a surface-hopping program for nonadiabatic molecular dynamics: Newton-X
  • Barbatti, Mario; Ruckenbauer, Matthias; Plasser, Felix
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1158
journal June 2013
Columbus-a program system for advanced multireference theory calculations: The Columbus multireference program system
  • Lischka, Hans; Müller, Thomas; Szalay, Péter G.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 2 https://doi.org/10.1002/wcms.25
journal January 2011
Excitation of Nucleobases from a Computational Perspective I: Reaction Paths book January 2013
Excitation of Nucleobases from a Computational Perspective II: Dynamics book January 2014
Advances in electronic structure theory book January 2005
Advances in electronic structure theory book January 2005
Applying the vibronic coupling model Hamiltonian to the photoelectron spectrum of cyclobutadiene journal October 2006
Using photoelectron spectroscopy to unravel the excited-state dynamics of benzene journal September 2007
Two- and three-state conical intersections in the uracil cation journal June 2008
Quaternions in molecular modeling journal January 2007
The on-the-fly surface-hopping program system Newton-X: Application to ab initio simulation of the nonadiabatic photodynamics of benchmark systems journal August 2007
Femtosecond Time-Resolved Photoelectron Spectroscopy journal April 2004
Accurate Anharmonic Vibrational Frequencies for Uracil: The Performance of Composite Schemes and Hybrid CC/DFT Model journal October 2011
The restricted active space self-consistent-field method, implemented with a split graph unitary group approach journal July 1990
The à 2 E/B̃ 2 B 2 Photoelectron Bands of Allene beyond the Linear Coupling Scheme:  An ab Initio Dynamical Study Including All Fifteen Vibrational Modes † journal June 2001
Radiationless Decay of Excited States of Uracil through Conical Intersections journal September 2004
Fragmentation Pathways in the Uracil Radical Cation journal September 2012
Ultrafast Relaxation Dynamics of Uracil Probed via Strong Field Dissociative Ionization journal November 2013
Photoelectron Spectrum and Dynamics of the Uracil Cation journal January 2015
Excited-State Diproton Transfer in [2,2′-Bipyridyl]-3,3′-diol: the Mechanism Is Sequential, Not Concerted journal July 2009
Photochemical Dynamics of Ethylene Cation C 2 H 4 + journal March 2014
Ion conformation and orientational order in a dicationic ionic liquid crystal studied by solid-state nuclear magnetic resonance spectroscopy journal March 2021
Advances in methods and algorithms in a modern quantum chemistry program package journal January 2006
Advances in methods and algorithms in a modern quantum chemistry program package journal January 2006
Combining dissociative ionization pump–probe spectroscopy and ab initio calculations to interpret dynamics and control through conical intersections journal January 2011
Characterization of electronic transitions in complex molecules journal January 1950
Ground state normal mode analysis: Linking excited state dynamics and experimental observables journal April 2001
All mode dynamics at the conical intersection of an octa-atomic molecule: Multi-configuration time-dependent Hartree (MCTDH) investigation on the butatriene cation journal August 2001
Multistate vibronic interactions in the benzene radical cation. II. Quantum dynamical simulations journal August 2002
Accidental conical intersections of three states of the same symmetry. I. Location and relevance journal October 2002
Critical appraisal of the fewest switches algorithm for surface hopping journal April 2007
Closed-loop learning control of isomerization using shaped ultrafast laser pulses in the deep ultraviolet journal April 2009
Conformationally selective photodissociation dynamics of propanal cation journal February 2011
Molecular dynamics with electronic transitions journal July 1990
Proton transfer in solution: Molecular dynamics with quantum transitions journal September 1994
Surface hopping dynamics using a locally diabatic formalism: Charge transfer in the ethylene dimer cation and excited state dynamics in the 2-pyridone dimer journal December 2012
Vibronic structure of the valence π-photoelectron bands in furan, pyrrole, and thiophene journal July 1998
High-resolution photoelectron spectra of the pyrimidine-type nucleobases journal June 2015
Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases journal November 2010
Strong field molecular ionization to multiple ionic states: direct versus indirect pathways journal June 2014
Removing electrons from more than one orbital: direct and indirect pathways to excited states of molecular cations journal October 2014
Dyson norms in XUV and strong-field ionization of polyatomics: Cytosine and uracil journal November 2012
Neutral-Ionic State Correlations in Strong-Field Molecular Ionization journal November 2012
The Ultrafast Pathway of Photon-Induced Electrocyclic Ring-Opening Reactions: The Case of 1,3-Cyclohexadiene journal May 2011
Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space journal May 2008

Cited By (3)

Computing the Ultrafast and Radiationless Electronic Excited State Decay of Cytosine and 5‐methyl‐cytosine Cations: Uncovering the Role of Dynamic Electron Correlation journal May 2019
Calculations of non-adiabatic couplings within equation-of-motion coupled-cluster framework: Theory, implementation, and validation against multi-reference methods journal January 2018
Ultraviolet relaxation dynamics in uracil: Time-resolved photoion yield studies using a laser-based thermal desorption source journal July 2018

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dissociation
Excited states
Ground states
Ionizaiton
Isomerization
Non adiabatic couplings
Non adiabatic reactions
Normal modes
Surface dynamics