{"data":{"id":"10.6084/m9.figshare.c.3265015","type":"dois","attributes":{"doi":"10.6084/m9.figshare.c.3265015","prefix":"10.6084","suffix":"m9.figshare.c.3265015","identifiers":[],"alternateIdentifiers":[],"creators":[{"name":"Seyedeh Leila Hashemi Dashtaki","affiliation":[],"nameIdentifiers":[]},{"name":"Shapour Ramazani","affiliation":[],"nameIdentifiers":[]}],"titles":[{"title":"Variational transition state theory with multidimensional tunnelling and kinetic isotope effects in the reactions of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eD and C\u003csub\u003e2\u003c/sub\u003eD\u003csub\u003e6\u003c/sub\u003e with .CCl\u003csub\u003e3\u003c/sub\u003e to produce CHCl\u003csub\u003e3\u003c/sub\u003e and CDCl\u003csub\u003e3\u003c/sub\u003e"}],"publisher":"Figshare","container":{},"publicationYear":2016,"subjects":[{"subject":"Biophysics"},{"subject":"Biochemistry"},{"subject":"29999 Physical Sciences not elsewhere classified","subjectScheme":"FOR"},{"subject":"FOS: Physical sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Physical sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Medicine"},{"subject":"Molecular Biology"},{"subject":"39999 Chemical Sciences not elsewhere classified","subjectScheme":"FOR"},{"subject":"FOS: Chemical sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Chemical sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Sociology"},{"subject":"FOS: Sociology","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Sociology","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"69999 Biological Sciences not elsewhere classified","subjectScheme":"FOR"},{"subject":"FOS: Biological sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Biological sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Inorganic Chemistry"},{"subject":"Infectious Diseases"},{"subject":"FOS: Health sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"FOS: Health sciences","subjectScheme":"Fields of Science and Technology (FOS)"}],"contributors":[],"dates":[{"date":"2016-06-03","dateType":"Created"},{"date":"2016-06-03","dateType":"Updated"},{"date":"2016","dateType":"Issued"}],"language":null,"types":{"ris":"GEN","bibtex":"misc","citeproc":"article","schemaOrg":"Collection","resourceType":"Collection","resourceTypeGeneral":"Collection"},"relatedIdentifiers":[{"relationType":"IsSupplementTo","relatedIdentifier":"10.1080/00268976.2016.1190875","relatedIdentifierType":"DOI"}],"relatedItems":[],"sizes":[],"formats":[],"version":null,"rightsList":[{"rights":"CC-BY","rightsUri":"http://creativecommons.org/licenses/by/3.0/us"}],"descriptions":[{"description":"Rate constants for the reactions of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eD and C\u003csub\u003e2\u003c/sub\u003eD\u003csub\u003e6\u003c/sub\u003e with \u003cb\u003e.\u003c/b\u003eCCl\u003csub\u003e3\u003c/sub\u003e. for the production of CHCl\u003csub\u003e3\u003c/sub\u003e and CDCl\u003csub\u003e3\u003c/sub\u003e (\u003ci\u003ek\u003c/i\u003e\u003csub\u003e1\u003c/sub\u003e, \u003ci\u003ek\u003c/i\u003e\u003csub\u003e2\u003c/sub\u003e, \u003ci\u003ek\u003c/i\u003e\u003csub\u003e3\u003c/sub\u003e and \u003ci\u003ek\u003c/i\u003e\u003csub\u003e4\u003c/sub\u003e) were computed using variational transition state theory coupled with hybrid-meta density functional theory (MPWB1K) over the temperature range of 200–2900 K. The ground-state vibrational adiabatic potential was plotted for all channels. Small- and large-curvature tunnelling were determined to include quantum effects in the calculation of rate constants. Harmonic vibrational frequencies along the reaction path were calculated in curvilinear coordinates with scaled frequencies. Anharmonicity was included in the lowest-frequency torsion. The position of formation and dissociation of bonds was specified using the variation in harmonic vibrational frequencies along the reaction path. Representative tunnelling energy and the thermally averaged transmission probability at 298 K (\u003ci\u003eP\u003c/i\u003e(\u003ci\u003eE\u003c/i\u003e)exp ( − Δ\u003ci\u003eE\u003c/i\u003e/\u003ci\u003eRT\u003c/i\u003e)) were determined for the reactions in which tunnelling is important. The kinetic isotope effect was used to calculate the considerable contributions of tunnelling and vibration. The expressions for rate constants were determined using nonlinear least-square fitting over the temperature range of 200–2900 K.","descriptionType":"Abstract"}],"geoLocations":[],"fundingReferences":[],"xml":"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