| Title | Predicting Nuclear Resonance Vibrational Spectra of [Fe(OEP)(NO)] |
| Authors | Peng, Qian Pavlik, Jeffrey W. Scheidt, W. Robert Wiest, Olaf |
| Affiliation | Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA. Peking Univ, Sch Chem Biol & Biotechnol, Shenzhen Grad Sch, Shenzhen 518055, Peoples R China. |
| Keywords | GENERALIZED-GRADIENT-APPROXIMATION EFFECTIVE CORE POTENTIALS DENSITY-FUNCTIONAL CALCULATIONS FERROUS HEME-NITROSYLS GAUSSIAN-BASIS SETS LYING SPIN STATES AXIAL LIGAND ELECTRONIC-STRUCTURE RAMAN-SPECTROSCOPY MOLECULAR CALCULATIONS |
| Issue Date | 2012 |
| Publisher | journal of chemical theory and computation |
| Citation | JOURNAL OF CHEMICAL THEORY AND COMPUTATION.2012,8,(1),214-223. |
| Abstract | Nuclear resonance vibrational spectroscopy (NRVS) is a sensitive vibrational probe for biologically important heme complexes. The exquisite sensitivity of the NRVS data to the electronic structure provides detailed insights into the nature of these interesting compounds but requires highly accurate computational methods for the mode assignments. To determine the best combinations of density functionals and basis sets, a series of benchmark DFT calculations on the previously characterized complex [Fe(OEP)NO] (OEP(2-) = octaethylporphyrinatio dianion) was performed. A test set of 21 methodology combinations including eight functionals (BP86, mPWPW91, B3LYP, PBE1PBE, M062X, M06L, LC-BP86, and omega B97X-D) and five basis set (VTZ, TZVP, and Lanl2DZ for iron and 6-3IG* and 6-31+G* for other atoms) was carried out to calculate electronic structures and vibrational frequencies. We also implemented the conversion of frequency calculations into orientation-selective mode composition factors (e(2)), which can be used to simulate the vibrational density of states (VDOS) using Gaussian normal distribution functions. These use a series of user-friendly scripts for their application to NRVS. The structures as well as the isotropic and anisotropic NRVS of [Fe (OEP)NO] obtained with the M06L functional with a variety of basis sets are found to best reproduce the available experimental data, followed by B3LYP/LanL2DZ calculations. Other density functionals and basis sets do not produce the same level of accuracy. The noticeably worse agreement between theory and experiment for the out-of-plane NRVS compared with the excellent performance of the M06L functional for the in-plane prediction is attributed to deficiencies of the physical model rather than the computational methodology. |
| URI | http://hdl.handle.net/20.500.11897/236471 |
| ISSN | 1549-9618 |
| DOI | 10.1021/ct2006456 |
| Indexed | SCI(E) |
| Appears in Collections: | 化学生物学与生物技术学院 |
