Modeling nonadiabatic dynamics at molecule-metal interfaces / Wenjie Dou.

Format:

Book

Manuscript

Thesis/Dissertation

Author/Creator:

Dou, Wenjie, author.

Contributor:

Subotnik, Joseph E., degree supervisor.

Anna, Jessica M., degree committee member.

Lester, Marsha I., degree committee member.

Rappe, Andrew M., degree committee member.

University of Pennsylvania. Department of Chemistry, degree granting institution.

Language:

English

Subjects (All):

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Local Subjects:

Penn dissertations--Chemistry.

Chemistry--Penn dissertations.

Physical Description:

xviii, 214 leaves : illustrations ; 29 cm

Production:

[Philadelphia, Pennsylvania] : University of Pennsylvania, 2018.

Summary:

The coupled electronic-nuclear dynamics at molecule-metal interfaces are fundamental processes that underlie many distinct areas of science: from electrochemistry, chemisorption, heterogeneous catalysis, quantum dots, all the way to molecular conduction. Simulating these coupled dynamics at molecule-metal interfaces is very challenging, due to the breakdown of the Born-Oppenheimer approximation and the inclusion of a manifold of electrons from the metal. Two methods are presented to investigate these nonadiabatic dynamics: a) In the outer sphere regime (weak electronic coupling between molecule and metal), a surface hopping approach is developed to treat nuclear motion classically with electronic motion captured by hopping between different potential energy surfaces; b) In the inner sphere regime (strong electronic coupling between molecule and metal), electronic dynamics are incorporated into a frictional force (i.e. electronic friction) together with a random force. In addition, a natural combination of these two methods called a broadened classical master equation (BCME) is developed. As benchmarked against numerical exact solutions, the BCME works well in both inner and outer sphere regimes. Finally, a universal form of electronic friction is derived. Such a formula unifies many different forms of electronic friction in the literature and allows the inclusion of electron-electron interactions, and can demonstrate interesting Kondo resonances at low temperature.

Notes:

Ph. D. University of Pennsylvania 2018.

Department: Chemistry.

Supervisor: Joseph E. Subotnik.

Includes bibliographical references.