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

Title: Nonadiabatic tunneling via conical intersections and the role of the geometric phase

Journal Article · · Physical Review A
 [1];  [2];  [3]
  1. Univ. of New Mexico, Albuquerque, NM (United States); DOE/OSTI
  2. Johns Hopkins Univ., Baltimore, MD (United States)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
+ Show Author Affiliations

As a ubiquitous quantum effect, tunneling has attracted attention ever since the dawn of quantum mechanics. However, recent evidence suggests that nonadiabatic atomic tunneling near a conical intersection (CI) behaves differently from its adiabatic counterpart, producing lifetime differences of up to two orders of magnitude. Using two-dimensional models, we demonstrate here that the failure of the adiabatic model in describing tunneling near a CI can be attributed largely to the neglect of the geometric phase, which is associated with the adiabatic electronic wave function transported around a CI. Furthermore, the geometric phase–induced destructive interference among wave functions following different paths around the CI, manifested as a node in the adiabatic wave function, retards tunneling.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
SC0015997
OSTI ID:
1535725
Journal Information:
Physical Review A, Journal Name: Physical Review A Journal Issue: 2 Vol. 95; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (55)

First principles calculation of the potential energy surface for the lowest-quartet state of H3 and modelling by the double many-body expansion method journal January 2000
Geometric phase effects in dynamics near conical intersections: Symmetry breaking and spatial localization text January 2013
Beyond Born-Oppenheimer book January 2006
Multimode Molecular Dynamics Beyond the Born-Oppenheimer Approximation book January 2007
Zur Quantentheorie der Molekeln journal January 1927
Numerical study of the geometric phase in the H+H2 reaction journal March 1990
Topological effects in molecular systems: an attempt towards a complete theory journal September 2000
Investigation of geometric phase effects in photodissociation dynamics at a conical intersection journal October 2014
Observation of geometric phase effect induced photodissociation dynamics in phenol journal October 2008
Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling journal November 2014
Nonadiabatic Tunneling in Photodissociation of Phenol journal June 2016
Photoinduced Electron and Proton Transfer in Phenol and Its Clusters with Water and Ammonia † journal October 2001
The geometric phase controls ultracold chemistry journal July 2015
Full-dimensional potentials and state couplings and multidimensional tunneling calculations for the photodissociation of phenol journal January 2014
Accurate nonadiabatic dynamics journal January 2016
Geometric phase effects on transition-state resonances and bound vibrational states of H3 via a time-dependent wavepacket method journal January 1997
O–H bond fission in 4-substituted phenols: S1 state predissociation viewed in a Hammett-like framework journal January 2013
Intersection of potential energy surfaces in polyatomic molecules journal January 1963
Cyclic-N3. II. Significant geometric phase effects in the vibrational spectra journal January 2005
Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol journal June 2005
Geometric phase effects in the H+H2 reaction: Quantum wave-packet calculations of integral and differential cross sections journal May 2005
General explanation of geometric phase effects in reactive systems: Unwinding the nuclear wave function using simple topology journal February 2006
Strong geometric-phase effects in the hydrogen-exchange reaction at high collision energies journal March 2008
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
Tunnelling under a conical intersection: Application to the product vibrational state distributions in the UV photodissociation of phenols journal May 2011
On the determination of Born–Oppenheimer nuclear motion wave functions including complications due to conical intersections and identical nuclei journal March 1979
Superposition of reactive and nonreactive scattering amplitudes in the presence of a conical intersection journal March 1980
Conditions for the definition of a strictly diabatic electronic basis for molecular systems journal December 1982
An accurate and efficient scheme for propagating the time dependent Schrödinger equation journal November 1984
A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method journal February 1992
The geometric phase in two electronic level systems journal September 1994
Geometric phase effects and wave packet dynamics on intersecting potential energy surfaces journal December 1995
Anomalous symmetries of the rovibrational states of HO 2 : Consequences of a conical intersection journal September 1995
Geometric phase effects in H+O 2 scattering. I. Surface function solutions in the presence of a conical intersection journal May 1996
A study of conical intersection effects on scattering processes: The validity of adiabatic single‐surface approximations within a quasi‐Jahn–Teller model journal November 1996
On the consequences of nonremovable derivative couplings. I. The geometric phase and quasidiabatic states: A numerical study journal December 1996
On the Longuet-Higgins phase and its relation to the electronic adiabatic–diabatic transformation angle journal August 1997
On phase factors and geometric phases in isotopes of H3: A line integral study journal February 2000
Geometric phase effects in the H+D2→HD+D reaction journal April 2000
Geometric phase effects in low-energy dynamics near conical intersections: A study of the multidimensional linear vibronic coupling model journal December 2013
When do we need to account for the geometric phase in excited state dynamics? journal June 2014
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
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 incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data journal December 2016
Studies of the Jahn-Teller effect .II. The dynamical problem
  • Longuet-Higgins, Hugh Christopher; Öpik, U.; Lecorney Pryce, Maurice Henry
  • Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 244, Issue 1236, p. 1-16 https://doi.org/10.1098/rspa.1958.0022
journal February 1958
Quantal Phase Factors Accompanying Adiabatic Changes journal March 1984
Diabatic and Adiabatic Representations for Atomic Collision Problems journal March 1969
Geometric Phase Effects in Dynamics Near Conical Intersections: Symmetry Breaking and Spatial Localization journal November 2013
Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction journal October 2015
Berry’s geometrical phase and the sequence of states in the Jahn-Teller effect journal February 1987
Geometric Phase Effects in the Vibrational Spectrum of Na 3 ( X ) journal September 1997
Diabolical conical intersections journal October 1996
Theoretical Study of Geometric Phase Effects in the Hydrogen-Exchange Reaction journal August 2005
The Role of   * Excited States in the Photodissociation of Heteroaromatic Molecules journal June 2006
Conical Intersections: Electronic Structure, Dynamics and Spectroscopy book July 2004

Cited By (10)

Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects journal September 2018
Intrinsic and light-induced nonadiabatic phenomena in the NaI molecule journal January 2017
Diabatic states, nonadiabatic coupling, and the counterpoise procedure for weakly interacting open-shell molecules journal March 2018
Non-adiabatic quantum reactive scattering in hyperspherical coordinates journal January 2018
Geometric phase effects on photodissociation dynamics of diatomics journal December 2018
A discontinuous basis enables numerically exact solution of the Schrödinger equation around conical intersections in the adiabatic representation journal February 2019
Vibronic coupling in the F·CH 4 prereactive complex journal September 2019
Triplet vs πσ* state mediated N–H dissociation of aniline journal October 2019
Continuous vibronic symmetries in Jahn–Teller models journal July 2018
Interplay of electron-phonon nonadiabaticity and Raman scattering in the wavepacket dynamics of electron-phonon-photon systems journal June 2019

Similar Records

Up to a Sign. The Insidious Effects of Energetically Inaccessible Conical Intersections on Unimolecular Reactions
Journal Article · 2019 · Accounts of Chemical Research · OSTI ID:1596716
+1 more
Diabolical conical intersections
Journal Article · 1996 · Reviews of Modern Physics · OSTI ID:388480
Wave function continuity and the diagonal Born-Oppenheimer correction at conical intersections
Journal Article · 2016 · Journal of Chemical Physics · OSTI ID:22657981

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical reactions
photodissociation