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UNO DMRG CAS CI calculations of binuclear manganese complex Mn(IV)2O2(NHCHCO2)4: Scope and applicability of Heisenberg model |
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| Authors: | Takashi Kawakami Koichi Miyagawa Sandeep Sharma Toru Saito Mitsuo Shoji Satoru Yamada Shusuke Yamanaka Mitsutaka Okumura Takahito Nakajima Kizashi Yamaguchi |
| Affiliation: | 1. Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043 Japan;2. The Institute of Scientific and Industrial Research, Osaka University, Osaka, Ibaraki, 567-0047 Japan;3. Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado, 80309;4. Graduate School of Information Sciences, Hiroshima City University, Hiroshima, 731-3194 Japan;5. Center of Computational Sciences, University of Tsukuba, Tsukuba, Ibaraki, 305-8577 Japan;6. Riken Center for Computational Science, Kobe, Hyogo, 650-0047 Japan;7. Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043 Japan Riken Center for Computational Science, Kobe, Hyogo, 650-0047 Japan The Institute of Scientific and Industrial Research, Osaka University, Osaka, Ibaraki, 567-0047 Japan NanoScience Design Center, Osaka University, Toyonaka, Osaka, 560-8531 Japan |
| Abstract: | Both direct exchange and super-exchange interactions cooperate to realize inter-spin magnetic interaction in binuclear manganese complex Mn(IV)2O2(NHCHCO2)4 with a di-μ-oxo path. We revisited this spin system using DMRG CAS methods and CAS selection procedures. Our results indicate that our previous “dynamically extended spin polarization” (DE-SP) procedure for organic polyradicals and so forth does not work well. Thus, we have examined another selection procedure, the “dynamically extended super-exchange” (DE-SE) procedure. DMRG CASCI [18,18] by UB3LYP(HS)-UNO(DE-SE) can realize antiferromagnetic J values similar to experimental ones (−87 cm−1). In addition, all J values between all spin states (HS[septet],IS[quintet],IS[triplet],LS[singlet])were also shown to be correct under sufficiently large M values. © 2018 Wiley Periodicals, Inc. |
| Keywords: | CaMn4O5 cluster binuclear manganese complex magnetic interaction DMRG CAS active orbital selection |