Influence on isotope effect calculations of the method of obtaining force constants from vibrational data
Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly...
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| Veröffentlicht in: | J. Phys. Chem.; (United States) 1982-03, Vol.86 (5), p.659-663 |
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| container_title | J. Phys. Chem.; (United States) |
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| creator | Goodson, David Z Sarpal, S. K Bopp, Philippe Wolfsberg, Max |
| description | Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly deduced from observed fundamentals in vibrational spectra and the (s/sub 2//s/sub 1/)f values so obtained are labeled (ANHARM). In a theroretically more valid procedure that is more difficult, one corrects observed fundamentals for anharmonicity on the basis of observed overtone and combination bands and then deduces force constants from these observed harmonic frequencies. The (s/sub 2//s/sub 1/)f values obtained from these force constants are labeled (HARM). (HARM) values and (ANHARM) values are evaluated and the isotope effects calculated with these values are discussed. It is concluded that the consistent use of (ANHARM) values in such calculations is a valid procedure. |
| doi_str_mv | 10.1021/j100394a014 |
| format | Article |
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K ; Bopp, Philippe ; Wolfsberg, Max</creator><creatorcontrib>Goodson, David Z ; Sarpal, S. K ; Bopp, Philippe ; Wolfsberg, Max ; Univ. of California, Irvine</creatorcontrib><description>Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly deduced from observed fundamentals in vibrational spectra and the (s/sub 2//s/sub 1/)f values so obtained are labeled (ANHARM). In a theroretically more valid procedure that is more difficult, one corrects observed fundamentals for anharmonicity on the basis of observed overtone and combination bands and then deduces force constants from these observed harmonic frequencies. The (s/sub 2//s/sub 1/)f values obtained from these force constants are labeled (HARM). (HARM) values and (ANHARM) values are evaluated and the isotope effects calculated with these values are discussed. It is concluded that the consistent use of (ANHARM) values in such calculations is a valid procedure.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j100394a014</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400302 -- Organic Chemistry-- Isotope Effects-- (-1987) ; BORN-OPPENHEIMER APPROXIMATION ; CALCULATION METHODS ; CORRECTIONS ; DEUTERIUM ; ENERGY LEVELS ; EQUILIBRIUM ; EXCITED STATES ; FUNCTIONS ; HARMONIC POTENTIAL ; HYDROGEN ISOTOPES ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ISOTOPE EFFECTS ; ISOTOPES ; LABELLED COMPOUNDS ; LIGHT NUCLEI ; MEDIUM TEMPERATURE ; NUCLEAR POTENTIAL ; NUCLEI ; ODD-ODD NUCLEI ; PARTITION FUNCTIONS ; POTENTIALS ; STABLE ISOTOPES 400202 -- Isotope Effects, Isotope Exchange, & Isotope Separation ; THERMAL EQUILIBRIUM ; VIBRATIONAL STATES</subject><ispartof>J. Phys. 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K</creatorcontrib><creatorcontrib>Bopp, Philippe</creatorcontrib><creatorcontrib>Wolfsberg, Max</creatorcontrib><creatorcontrib>Univ. of California, Irvine</creatorcontrib><title>Influence on isotope effect calculations of the method of obtaining force constants from vibrational data</title><title>J. Phys. Chem.; (United States)</title><addtitle>J. Phys. Chem</addtitle><description>Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly deduced from observed fundamentals in vibrational spectra and the (s/sub 2//s/sub 1/)f values so obtained are labeled (ANHARM). In a theroretically more valid procedure that is more difficult, one corrects observed fundamentals for anharmonicity on the basis of observed overtone and combination bands and then deduces force constants from these observed harmonic frequencies. The (s/sub 2//s/sub 1/)f values obtained from these force constants are labeled (HARM). (HARM) values and (ANHARM) values are evaluated and the isotope effects calculated with these values are discussed. It is concluded that the consistent use of (ANHARM) values in such calculations is a valid procedure.</description><subject>400302 -- Organic Chemistry-- Isotope Effects-- (-1987)</subject><subject>BORN-OPPENHEIMER APPROXIMATION</subject><subject>CALCULATION METHODS</subject><subject>CORRECTIONS</subject><subject>DEUTERIUM</subject><subject>ENERGY LEVELS</subject><subject>EQUILIBRIUM</subject><subject>EXCITED STATES</subject><subject>FUNCTIONS</subject><subject>HARMONIC POTENTIAL</subject><subject>HYDROGEN ISOTOPES</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ISOTOPE EFFECTS</subject><subject>ISOTOPES</subject><subject>LABELLED COMPOUNDS</subject><subject>LIGHT NUCLEI</subject><subject>MEDIUM TEMPERATURE</subject><subject>NUCLEAR POTENTIAL</subject><subject>NUCLEI</subject><subject>ODD-ODD NUCLEI</subject><subject>PARTITION FUNCTIONS</subject><subject>POTENTIALS</subject><subject>STABLE ISOTOPES 400202 -- Isotope Effects, Isotope Exchange, & Isotope Separation</subject><subject>THERMAL EQUILIBRIUM</subject><subject>VIBRATIONAL STATES</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1982</creationdate><recordtype>article</recordtype><recordid>eNpt0E1LAzEQBuAgCtbqyT8QvHiQ1ckm2W2OUj-qFBQ_Ll7CbJrY1O1GklT037taEQ-ehoFnhpmXkH0GxwxKdrJgAFwJBCY2yIBJwQpZC9gkA4CyLHglxTbZSWkBAIxzNiD-qnPtynbG0tBRn0IOr5Za56zJ1GBrVi1mH7pEg6N5bunS5nmYfXWhyeg73z1TF2I_b3qVscuJuhiW9M038XsUWzrDjLtky2Gb7N5PHZLHi_OH8aSY3lxejU-nBXIOuXDWukZWEiSziqnSgcKqFrNaKW4ssmo2QlCi4eh47UxTl1KMQHFbNo0oS-RDcrDeG1L2OhmfrZn3t3X9R7oaMVWNqh4drZGJIaVonX6NfonxQzPQX1HqP1H2ulhrn7J9_6UYX3RV81rqh9t7fSYnT3fT6zvNen-49miSXoRV7DNI_27-BDENgqw</recordid><startdate>19820301</startdate><enddate>19820301</enddate><creator>Goodson, David Z</creator><creator>Sarpal, S. K</creator><creator>Bopp, Philippe</creator><creator>Wolfsberg, Max</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19820301</creationdate><title>Influence on isotope effect calculations of the method of obtaining force constants from vibrational data</title><author>Goodson, David Z ; Sarpal, S. K ; Bopp, Philippe ; Wolfsberg, Max</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a330t-feefb565051e9192f09a674d7993cea16d8a094b3af37fcb72548093e2bb422a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1982</creationdate><topic>400302 -- Organic Chemistry-- Isotope Effects-- (-1987)</topic><topic>BORN-OPPENHEIMER APPROXIMATION</topic><topic>CALCULATION METHODS</topic><topic>CORRECTIONS</topic><topic>DEUTERIUM</topic><topic>ENERGY LEVELS</topic><topic>EQUILIBRIUM</topic><topic>EXCITED STATES</topic><topic>FUNCTIONS</topic><topic>HARMONIC POTENTIAL</topic><topic>HYDROGEN ISOTOPES</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ISOTOPE EFFECTS</topic><topic>ISOTOPES</topic><topic>LABELLED COMPOUNDS</topic><topic>LIGHT NUCLEI</topic><topic>MEDIUM TEMPERATURE</topic><topic>NUCLEAR POTENTIAL</topic><topic>NUCLEI</topic><topic>ODD-ODD NUCLEI</topic><topic>PARTITION FUNCTIONS</topic><topic>POTENTIALS</topic><topic>STABLE ISOTOPES 400202 -- Isotope Effects, Isotope Exchange, & Isotope Separation</topic><topic>THERMAL EQUILIBRIUM</topic><topic>VIBRATIONAL STATES</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Goodson, David Z</creatorcontrib><creatorcontrib>Sarpal, S. K</creatorcontrib><creatorcontrib>Bopp, Philippe</creatorcontrib><creatorcontrib>Wolfsberg, Max</creatorcontrib><creatorcontrib>Univ. of California, Irvine</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Goodson, David Z</au><au>Sarpal, S. K</au><au>Bopp, Philippe</au><au>Wolfsberg, Max</au><aucorp>Univ. of California, Irvine</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Influence on isotope effect calculations of the method of obtaining force constants from vibrational data</atitle><jtitle>J. Phys. Chem.; (United States)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1982-03-01</date><risdate>1982</risdate><volume>86</volume><issue>5</issue><spage>659</spage><epage>663</epage><pages>659-663</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><abstract>Reduced isotopic partition function ratios (s/sub 2//s/sub 1/)f are employed in the calculation of isotope effects on thermodynamic equilibrium constrants. The quadratic force constants of the molecular force field are needed to evaluate (s/sub 2//s/sub 1/)f. Often these force constants are directly deduced from observed fundamentals in vibrational spectra and the (s/sub 2//s/sub 1/)f values so obtained are labeled (ANHARM). In a theroretically more valid procedure that is more difficult, one corrects observed fundamentals for anharmonicity on the basis of observed overtone and combination bands and then deduces force constants from these observed harmonic frequencies. The (s/sub 2//s/sub 1/)f values obtained from these force constants are labeled (HARM). (HARM) values and (ANHARM) values are evaluated and the isotope effects calculated with these values are discussed. It is concluded that the consistent use of (ANHARM) values in such calculations is a valid procedure.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/j100394a014</doi><tpages>5</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0022-3654 |
| ispartof | J. Phys. Chem.; (United States), 1982-03, Vol.86 (5), p.659-663 |
| issn | 0022-3654 1541-5740 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_j100394a014 |
| source | American Chemical Society Journals |
| subjects | 400302 -- Organic Chemistry-- Isotope Effects-- (-1987) BORN-OPPENHEIMER APPROXIMATION CALCULATION METHODS CORRECTIONS DEUTERIUM ENERGY LEVELS EQUILIBRIUM EXCITED STATES FUNCTIONS HARMONIC POTENTIAL HYDROGEN ISOTOPES INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ISOTOPE EFFECTS ISOTOPES LABELLED COMPOUNDS LIGHT NUCLEI MEDIUM TEMPERATURE NUCLEAR POTENTIAL NUCLEI ODD-ODD NUCLEI PARTITION FUNCTIONS POTENTIALS STABLE ISOTOPES 400202 -- Isotope Effects, Isotope Exchange, & Isotope Separation THERMAL EQUILIBRIUM VIBRATIONAL STATES |
| title | Influence on isotope effect calculations of the method of obtaining force constants from vibrational data |
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