Solvent Dependence of Double Proton Transfer in the Formic Acid

Sep 6, 2017 - Graduate School of Arts and Science, The University of Tokyo, 4-6-1 Komaba, Meguroku, Tokyo 153-8902, Japan .... (17) who employed Carâ€...
0 downloads 9 Views 2MB Size
Subscriber access provided by Duke University Libraries

Article

Solvent Dependence of Double Proton Transfer in the Formic Acid Formamidine Complex: Path Integral Molecular Dynamics Investigation Nawee Kungwan, Chanisorn Ngaojampa, Yudai Ogata, Tsutomu Kawatsu, Yuki Oba, Yukio Kawashima, and Masanori Tachikawa J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b07010 • Publication Date (Web): 06 Sep 2017 Downloaded from http://pubs.acs.org on September 11, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

The Journal of Physical Chemistry A is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 35

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

Solvent Dependence of Double Proton Transfer in the Formic Acid - Formamidine Complex: Path Integral Molecular Dynamics Investigation

Nawee Kungwana,b*, Chanisorn Ngaojampaa,b, Yudai Ogatac, Tsutomu Kawatsuc,d, Yuki Obac, Yukio Kawashimae and Masanori Tachikawac,*

a

Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

b

Center of Excellence in Materials Science and Technology, Chiang Mai University, Thailand c

Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Yokohama-City, Kanagawa 236-0027, Japan d

Graduate School of Arts and Science, The University of Tokyo, 4-6-1 Komaba, Meguroku, Tokyo 153-8902, Japan

e

Advanced Institute for Computational Science, RIKEN,7-1-26 Minatojima-minami-machi, Chuo-ku, Kobe, Hyogo 650-0047, Japan

*

Corresponding

author. E-mail: [email protected] (N. Kungwan) and

tachi@yokohama-

cu.ac.jp (M. Tachikawa). Fax: +66 53 892 277 and +81 48 858 3700

1 ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 35

ABSTRACT Solvent dependence of double proton transfer in the formic acid–formamidine (FA-FN) complex at room temperature was investigated by means of ab initio path integral molecular dynamics (AIPIMD) simulation with taking nuclear quantum and thermal effects into account.

The

conductor-like screening model (COSMO) was applied for solvent effect. In comparison with gas phase, double proton delocalization between two heavy atoms (O and N) in FA-FN were observed with reduced proton transfer barrier height in low dielectric constant medium (4.8), the ionic species becomes more stable than the neutral ones and the formate anion and formamidium cation are thermodynamically stable. For ab initio molecular dynamics simulation, in low dielectric constant medium (