Including quantum effects in the dynamics of complex (i.e., large) molecular systems

Semiclassical instanton theory is used to study the quantum effects of tunnelling and delocalization in molecular systems. An analysis of the approximations involved in the method is presented based on a recent first-principles derivation of instanton rate theory [J. Chem. Phys., 2016,144, 114106]. It is known that the standard instanton method is unable to accurately compute thermal rates near the crossover temperature. The causes of this problem are identified and an improved method is proposed, whereby an instanton approximation to the microcanonical rate is defined and integrated numerically to obtain a thermal rate at any temperature. No new computational algorithms are required, but only data analysis of a number of standard instanton calculations.

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The Initial Value Representation of Semiclassical Theory: A Practical Way for Adding Quantum Effects to Classical Molecular Dynamics Simulations of Complex Molecular Systems

Physical Biology ◽

10.1142/9781848162013_0020 ◽

2008 ◽

pp. 505-525 ◽

Cited By ~ 2

Author(s):

William H. Miller

Keyword(s):

Molecular Dynamics ◽

Molecular Dynamics Simulations ◽

Quantum Effects ◽

Semiclassical Theory ◽

Initial Value ◽

Molecular Systems ◽

Classical Molecular Dynamics ◽

Initial Value Representation ◽

Dynamics Simulations ◽

Value Representation

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Highlights from the Faraday Discussion 296: quantum effects in small molecular systems, 10–12 September 2018, Edinburgh, United Kingdom

Chemical Communications ◽

10.1039/c8cc90523a ◽

2018 ◽

Vol 54 (97) ◽

pp. 13620-13625

Author(s):

Loren Ban ◽

Matthieu Besemer ◽

Halima Mouhib

Keyword(s):

United Kingdom ◽

Quantum Effects ◽

Molecular Systems ◽

The Impact

Exciting discussions on the impact of quantum effects in small molecular systems took place in the historical city of Edinburgh this fall 2018 in the unique conference format of the Faraday Discussions.

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Concluding remarks

Faraday Discussions ◽

10.1039/c8fd90054j ◽

2018 ◽

Vol 212 ◽

pp. 603-607

Author(s):

Ad van der Avoird

Keyword(s):

Quantum Effects ◽

Molecular Systems

The Faraday Discussion on quantum effects in small molecular systems was held on 10th – 12th September 2018 in Edinburgh, UK. It reflected a wide variety of new theoretical and experimental developments, which provide insights and methods applicable to larger systems as well.

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