DOI: 10.1063/1.472580. Activated barrier crossing dynamics in slow, viscous liquids

Activated barrier crossing dynamics in slow, viscous liquids

10.1063/1.472580

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Experimental studies of reaction rates in slow, viscous liquids have often led to results at variance with conventional theoretical approaches. Here we present a self-consistent microscopic calculation of the rate which uses for the first time, the mode coupling theory (MCT) to obtain the frequency dependent friction. When this microscopic expression for the friction is used to obtain the barrier crossing rate from the Grote–Hynes (G–H) formula, the following results are found. At intermediate viscosities, the calculated rate exhibits a fractional viscosity dependence with parameter values in agreement with the experimental results. For example, we find an exponent equal to 0.8 when the barrier frequency (ωb) is equal to 2×1013 s−1, whereas the earlier calculations obtained an unrealistic value (close to 0.1) for this value of the barrier frequency. At very high viscosities we find an inverse logarithmic dependence of the rate on viscosity. This prediction can be tested against experiments.

Authors 2

Ranjit Biswas (first)
Biman Bagchi (additional)

References 52 Referenced 34

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Dates

Type	When
Created	23 years ago (July 26, 2002, 8:15 a.m.)
Deposited	2 years, 1 month ago (June 30, 2023, 10:23 a.m.)
Indexed	1 year, 3 months ago (May 1, 2024, 6:32 a.m.)
Issued	28 years, 9 months ago (Nov. 1, 1996)
Published	28 years, 9 months ago (Nov. 1, 1996)
Published Print	28 years, 9 months ago (Nov. 1, 1996)

Funders 0

None

BibTeX

@article{Biswas_1996, title={Activated barrier crossing dynamics in slow, viscous liquids}, volume={105}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.472580}, DOI={10.1063/1.472580}, number={17}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Biswas, Ranjit and Bagchi, Biman}, year={1996}, month=nov, pages={7543–7549} }

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          11,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.472580",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1996,
        11,
        1
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1996,
        11,
        1
      ]
    ]
  }
}