Perspective: Nonadiabatic dynamics theory

Tully, John C.

doi:10.1063/1.4757762

Cited by 549 publications

(593 citation statements)

References 80 publications

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“…1 These dynamics describe the motion of nuclei in systems in which the BornOppenheimer approximation is not valid. This could occur, for instance, at a conical intersection between two electronic states, 2,3 or as we consider here, near an avoided crossing.…”

Section: Introductionmentioning

confidence: 99%

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Richardson

Thoss

2014

The Journal of Chemical Physics

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Quantum mechanical canonical rate theory: A new approach based on the reactive flux and numerical analytic continuation methods J. Chem. Phys. 112, 2605 (2000); 10.1063/1.480834Erratum: "A unified framework for quantum activated rate processes. II. The nonadiabatic limit" [J. Chem. Phys. 106, 1769 There is currently much interest in the development of improved trajectory-based methods for the simulation of nonadiabatic processes in complex systems. An important goal for such methods is the accurate calculation of the rate constant over a wide range of electronic coupling strengths and it is often the nonadiabatic, weak-coupling limit, which being far from the Born-Oppenheimer regime, provides the greatest challenge to current methods. We show that in this limit there is an inherent sign problem impeding further development which originates from the use of the usual quantum flux correlation functions, which can be very oscillatory at short times. From linear response theory, we derive a modified flux correlation function for the calculation of nonadiabatic reaction rates, which still rigorously gives the correct result in the long-time limit regardless of electronic coupling strength, but unlike the usual formalism is not oscillatory in the weak-coupling regime. In particular, a trajectory simulation of the modified correlation function is naturally initialized in a region localized about the crossing of the potential energy surfaces. In the weak-coupling limit, a simple link can be found between the dynamics initialized from this transition-state region and an generalized quantum goldenrule transition-state theory, which is equivalent to Marcus theory in the classical harmonic limit. This new correlation function formalism thus provides a platform on which a wide variety of dynamical simulation methods can be built aiding the development of accurate nonadiabatic rate theories applicable to complex systems. © 2014 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 99%

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Richardson

Thoss

2014

The Journal of Chemical Physics

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“…Combined with a 50% absorption probability for a single photon by an ensemble of rhodopsin molecules contained within a rod cell [20], the overall process results in a remarkable ∼ 30% probability of detection of single photons. While the electronic and vibrational degrees of freedom are expected to be entangled around the conical intersection [21], it is not clear what role, if any, the underlying quantum correlations play for the creation of the signalling trans state.…”

Section: B Photo-activated Isomerization In Visionmentioning

confidence: 99%

Photoactivated biological processes as quantum measurements

İmamoğlu

2015

Phys. Rev. E

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We outline a framework for describing photo-activated biological reactions as generalized quantum measurements of external fields, for which the biological system takes on the role of a quantum meter. By using general arguments regarding the Hamiltonian that describes the measurement interaction, we identify the cases where it is essential for a complex chemical or biological system to exhibit non-equilibrium quantum coherent dynamics in order to achieve the requisite functionality. We illustrate the analysis by considering measurement of the solar radiation field in photosynthesis and measurement of the earth's magnetic field in avian magnetoreception.

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“…Non-BOA transitions pose challenges to both theory and experiment. From a theoretical point of view, excited state dynamics and nonadiabatic transitions both are difficult problems [2,3] (see Figure 1(a)). However, the theory on non-BOA dynamics has advanced significantly over the last two decades.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Soft X-ray Probing of Gas Phase Molecular Dynamics

Gühr

2016

Synchrotron Radiation News

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Perspective: Nonadiabatic dynamics theory

Cited by 549 publications

References 80 publications

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Photoactivated biological processes as quantum measurements

Ultrafast Soft X-ray Probing of Gas Phase Molecular Dynamics

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