skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: First-order derivative couplings between excited states from adiabatic TDDFT response theory

Journal Article · · The Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4906941· OSTI ID:1228544
 [1]; ORCiD logo [2];  [2];  [1]
  1. Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA
  2. Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA
+ Show Author Affiliations

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0008694
OSTI ID:
1228544
Journal Information:
The Journal of Chemical Physics, Journal Name: The Journal of Chemical Physics Vol. 142 Journal Issue: 6; ISSN 0021-9606
Publisher:
American Institute of PhysicsCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 71 works
Citation information provided by
Web of Science

References (34)

Derivative couplings between TDDFT excited states obtained by direct differentiation in the Tamm-Dancoff approximation journal July 2014
First-order nonadiabatic couplings from time-dependent hybrid density functional response theory: Consistent formalism, implementation, and performance journal January 2010
First order nonadiabatic coupling matrix elements between excited states: Implementation and application at the TD-DFT and pp-TDA levels journal December 2014
Nonadiabatic couplings from the Kohn-Sham derivative matrix: Formulation by time-dependent density-functional theory and evaluation in the pseudopotential framework journal December 2010
Nonadiabatic coupling vectors for excited states within time-dependent density functional theory in the Tamm–Dancoff approximation and beyond journal November 2010
Trajectory Surface Hopping within Linear Response Time-Dependent Density-Functional Theory journal January 2007
Derivative Couplings between Time-Dependent Density Functional Theory Excited States in the Random-Phase Approximation Based on Pseudo-Wavefunctions: Behavior around Conical Intersections journal August 2014
First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels journal July 2014
Excited-state potential energy curves from time-dependent density-functional theory: A cross section of formaldehyde's1A1 manifold journal January 1998
Q-Chem 2.0: a high-performanceab initio electronic structure program package journal January 2000
On the evaluation of nonadiabatic coupling matrix elements using SA‐MCSCF/CI wave functions and analytic gradient methods. I journal November 1984
Nonadiabatic couplings from time-dependent density functional theory. II. Successes and challenges of the pseudopotential approximation journal April 2008
Nonadiabatic couplings from time-dependent density functional theory: Formulation in the Casida formalism and practical scheme within modified linear response journal August 2007
On the evaluation of analytic energy derivatives for correlated wave functions journal December 1984
Density-Functional Theory for Time-Dependent Systems journal March 1984
Non-adiabatic dynamics using time-dependent density functional theory: Assessing the coupling strengths journal November 2009
Analytic derivative couplings in time-dependent density functional theory: Quadratic response theory versus pseudo-wavefunction approach journal February 2015
On the density matrix based approach to time-dependent density functional response theory journal April 2001
Double excitations within time-dependent density functional theory linear response journal April 2004
On the evaluation of non-adiabatic coupling matrix elements for large scale CI wavefunctions journal January 1985
Analytic derivative couplings for spin-flip configuration interaction singles and spin-flip time-dependent density functional theory journal August 2014
Density-matrix representation of nonadiabatic couplings in time-dependent density functional (TDDFT) theories journal February 2000
Analytic derivative couplings between configuration-interaction-singles states with built-in electron-translation factors for translational invariance journal December 2011
Nonadiabatic dynamics within the time dependent density functional theory: Ultrafast photodynamics in pyrazine journal June 2008
Analytic evaluation of nonadiabatic coupling terms at the MR-CI level. I. Formalism journal April 2004
Non-adiabatic couplings by time-dependent density functional theory journal September 2002
On correlated electron-nuclear dynamics using time-dependent density functional theory journal July 2006
Quadratic response functions within the time-dependent Hartree-Fock approximation journal July 1982
Ab initio non-adiabatic molecular dynamics journal January 2013
Optimizing Conical Intersections without Derivative Coupling Vectors:  Application to Multistate Multireference Second-Order Perturbation Theory (MS-CASPT2) † journal January 2008
On the evaluation of nonadiabatic coupling matrix elements for MCSCF/CI wave functions using analytic derivative methods. III. Second derivative terms journal January 1986
Fundamentals of Time-Dependent Density Functional Theory book January 2012
Calculating Derivative Couplings between Time-Dependent Hartree–Fock Excited States with Pseudo-Wavefunctions journal August 2014
Conical intersections and double excitations in time-dependent density functional theory journal March 2006

Similar Records

First-order derivative couplings between excited states from adiabatic TDDFT response theory
Journal Article · Sat Feb 14 00:00:00 EST 2015 · Journal of Chemical Physics · OSTI ID:1228544
Derivative couplings between TDDFT excited states obtained by direct differentiation in the Tamm-Dancoff approximation
Journal Article · Mon Jul 14 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:1228544
+1 more
Most theoretical approaches used in nuclear astrophysics to model the nucleosynthesis of heavy elements incorporate the so-called statistical model in order to describe the excitation and decay properties of atomic nuclei. One of the basic assumptions of this model is the validity of the Brink–Axel hypothesis and the related concept of so-called photon strength functions to describe γ-ray transition probabilities. We present a novel experimental approach that allows for the first time to experimentally determine the photon strength function simultaneously in two independent ways by a unique combination of quasi-monochromatic photon beams and a newly implemented γ–γ coincidence setup. This technique does not assume a priori the validity of the Brink–Axel hypothesis and sets a benchmark in terms of the detection sensitivity for measuring decay properties of photo-excited states below the neutron separation energy. The data for the spherical off-shell nucleus 128Te were obtained for γ-ray beam-energy settings between 3 MeV and 9 MeV in steps of 130 keV for the lower beam energies and in steps of up to 280 keV for the highest beam settings. We present a quantitative analysis on the consistency of the derived photon strength function with the Brink–Axel hypothesis. The data clearly demonstrate a discrepancy of up to a factor of two between the photon strength functions extracted from the photoabsorption and photon emission process, respectively. In addition, we observe that the photon strength functions are not independent of the excitation energy, as usually assumed. Thus, we conclude, that the Brink–Axel hypothesis is not strictly fulfilled in the excitation-energy region below the neutron separation threshold (Sn = 8.78 MeV) for the studied case of 128Te.
Journal Article · Tue Jan 01 00:00:00 EST 2019 · Physics Letters B · OSTI ID:1228544
+10 more

Related Subjects