Photochemistry of methyltrioxorhenium revisited: A DFT/TD-DFT and CASSCF/MS-CASPT2 theoretical study

Paulo Jorge Costa; Maria José Calhorda; Julien Bossert; Chantal Daniel; Carlos C. Romão

doi:10.1021/om0603868

Photochemistry of methyltrioxorhenium revisited: A DFT/TD-DFT and CASSCF/MS-CASPT2 theoretical study

Paulo Jorge Costa, Maria José Calhorda, Julien Bossert, Chantal Daniel, Carlos C. Romão

Instituto de Tecnologia Química e Biológica António Xavier (ITQB)

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

The electronic structure of (CH₃)ReO₃ was reanalyzed by means of DFT calculations (ADF and Gaussian03 programs). TD-DFT calculations were carried out, using the DFT-optimized structure and several functionals, to assign the electronic excitations and interpret the dissociative behavior under irradiation. The agreement between calculated and experimental wavelengths was very good and could not be improved when using highly correlated methods (CASSCF/MS-CASPT2). The lowest energy transition at 260 nm was assigned to a LMCT from p O to Re d (π* Re-O), correcting the earlier empirical assignment. The second transition, experimentally observed at 240 nm, is assigned to a charge transfer from C and O to Re in TD-DFT, but the weight of the C participation drops significantly in the CASSCF/MS-CASPT2 approach. (C₂H₅)ReO₃ exhibits a similar behavior. On the other hand, for (C₆H₅)-ReO₃ and {C ₆H₃(CH₃)₃}ReO₃ the strong low-energy absorption results from a LMCT from the phenyl π* to d Re (π* Re-O), reproducing the experimental trends.

Original language	English
Pages (from-to)	5235-5241
Number of pages	7
Journal	Organometallics
Volume	25
Issue number	22
DOIs	https://doi.org/10.1021/om0603868
Publication status	Published - 23 Oct 2006

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title = "Photochemistry of methyltrioxorhenium revisited: A DFT/TD-DFT and CASSCF/MS-CASPT2 theoretical study",

abstract = "The electronic structure of (CH3)ReO3 was reanalyzed by means of DFT calculations (ADF and Gaussian03 programs). TD-DFT calculations were carried out, using the DFT-optimized structure and several functionals, to assign the electronic excitations and interpret the dissociative behavior under irradiation. The agreement between calculated and experimental wavelengths was very good and could not be improved when using highly correlated methods (CASSCF/MS-CASPT2). The lowest energy transition at 260 nm was assigned to a LMCT from p O to Re d (π* Re-O), correcting the earlier empirical assignment. The second transition, experimentally observed at 240 nm, is assigned to a charge transfer from C and O to Re in TD-DFT, but the weight of the C participation drops significantly in the CASSCF/MS-CASPT2 approach. (C2H5)ReO3 exhibits a similar behavior. On the other hand, for (C6H5)-ReO3 and {C 6H3(CH3)3}ReO3 the strong low-energy absorption results from a LMCT from the phenyl π* to d Re (π* Re-O), reproducing the experimental trends.",

author = "Costa, {Paulo Jorge} and Calhorda, {Maria Jos{\'e}} and Julien Bossert and Chantal Daniel and Rom{\~a}o, {Carlos C.}",

year = "2006",

month = oct,

day = "23",

doi = "10.1021/om0603868",

language = "English",

volume = "25",

pages = "5235--5241",

journal = "Organometallics",

issn = "0276-7333",

publisher = "ACS - American Chemical Society",

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T1 - Photochemistry of methyltrioxorhenium revisited

T2 - A DFT/TD-DFT and CASSCF/MS-CASPT2 theoretical study

AU - Costa, Paulo Jorge

AU - Calhorda, Maria José

AU - Bossert, Julien

AU - Daniel, Chantal

AU - Romão, Carlos C.

PY - 2006/10/23

Y1 - 2006/10/23

N2 - The electronic structure of (CH3)ReO3 was reanalyzed by means of DFT calculations (ADF and Gaussian03 programs). TD-DFT calculations were carried out, using the DFT-optimized structure and several functionals, to assign the electronic excitations and interpret the dissociative behavior under irradiation. The agreement between calculated and experimental wavelengths was very good and could not be improved when using highly correlated methods (CASSCF/MS-CASPT2). The lowest energy transition at 260 nm was assigned to a LMCT from p O to Re d (π* Re-O), correcting the earlier empirical assignment. The second transition, experimentally observed at 240 nm, is assigned to a charge transfer from C and O to Re in TD-DFT, but the weight of the C participation drops significantly in the CASSCF/MS-CASPT2 approach. (C2H5)ReO3 exhibits a similar behavior. On the other hand, for (C6H5)-ReO3 and {C 6H3(CH3)3}ReO3 the strong low-energy absorption results from a LMCT from the phenyl π* to d Re (π* Re-O), reproducing the experimental trends.

AB - The electronic structure of (CH3)ReO3 was reanalyzed by means of DFT calculations (ADF and Gaussian03 programs). TD-DFT calculations were carried out, using the DFT-optimized structure and several functionals, to assign the electronic excitations and interpret the dissociative behavior under irradiation. The agreement between calculated and experimental wavelengths was very good and could not be improved when using highly correlated methods (CASSCF/MS-CASPT2). The lowest energy transition at 260 nm was assigned to a LMCT from p O to Re d (π* Re-O), correcting the earlier empirical assignment. The second transition, experimentally observed at 240 nm, is assigned to a charge transfer from C and O to Re in TD-DFT, but the weight of the C participation drops significantly in the CASSCF/MS-CASPT2 approach. (C2H5)ReO3 exhibits a similar behavior. On the other hand, for (C6H5)-ReO3 and {C 6H3(CH3)3}ReO3 the strong low-energy absorption results from a LMCT from the phenyl π* to d Re (π* Re-O), reproducing the experimental trends.

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SN - 0276-7333

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ER -

Photochemistry of methyltrioxorhenium revisited: A DFT/TD-DFT and CASSCF/MS-CASPT2 theoretical study

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