1997 年度実績報告書

並列計算による分子クラスターの分光学と化学反応の研究

研究課題

研究課題/領域番号	09304057
研究種目	基盤研究(A)
研究機関	岡崎国立共同研究機構
研究代表者	岩田末廣岡崎国立共同研究機構, 分子科学研究所, 教授 (20087505)
研究分担者	池上努岡崎国立共同研究機構, 分子科学研究所, 助手 (80245612) 南部伸孝岡崎国立共同研究機構, 分子科学研究所, 助手 (00249955) 高見利也岡崎国立共同研究機構, 分子科学研究所, 助手 (10270472) 青柳睦岡崎国立共同研究機構, 分子科学研究所, 助教授 (00260026)
キーワード	化学反応理論 / 計算化学 / 理論化学
研究概要	a)2乗可積分関数を用いた光電子脱離断面積の計算方の基底関数として、箱型ポテンシャルの固有関数を用いることとし、必要な分子積分プログラムを開発した。X線非弾性散乱実験によって測定される静的構造因子を理論的に計算するプログラムを開発し、基底関数と電子相関の効果を系統的に調べた。高次の電子相関の必要性が明らかになった。b)モンテカルロMC法と非経験的分子軌道MO法と結合させて、M+(M=B)と(H2O)nのクラスターの反応を追跡した.さらに、X-(H2O)n(X=F,Cl,Br,I)系にもこの方法を応用し、クラスター構造と振動スペクトルの内部エネルギー依存性を明らかにした。また、多次元系に開発されたマルチカノニカル法を水2量体の熱力学量の計算に導入し、その方法の適応力を検討し、、熱力学量や構造因子の温度依存性を調べるのに強力な研究方法であることを実証した。これら一連の研究によって、MCとMOを結合する方法は適用限界を適切に判断するならば、様々な化学の問題に実用段階になったことが明らかになった.c)水クラスター負イオン(H2O)n-の構造を分子軌道法によって研究した。いわゆる双極子場束縛型に加えて、余剰電子が二つの水分子のOHに包まれる内部包含型ともいえる異性体がn=2,3から安定に存在し、垂直電子離脱エネルギー(VDE)も測定値に近い値となることを始めて示した。d)一次元結晶密度汎関数プログラムを新たに開発した。解析的1次エネルギー勾配法に必要な公式を導出し、実用的プログラムを完成した。ポリアセチレンとポリメチルイミン、ポリエチレンなどに応用した。e)Arn+クラスターの光解離過程を非断熱遷移分子動力学計算によって追跡し、そのn依存性や光エネルギー依存性から解離と原子蒸発の競争・競合関係を明らかにした。f)CaCN/CaNCのポテンシャルエネルギー曲面を精密に求め、その曲面上の量子力学的な波束動力学計算を実行し異性化過程を動的に追跡した。g)フラーレンの各種異性体の構造と振動周波数を制度高い非経験的分子軌道法によって計算し実験と比較した。また経験的ポテンシャルを使ってフラーレン集合体の運動を古典動力学計算で追跡した。

研究成果
(29件)

すべてその他

すべて文献書誌 (29件)

[文献書誌] C.-G.ZHAN and S.IWATA: "Theoretical prediction of the ^<31>P NMR chemical shift of the hexa-coordinate phosphorus intermediate for the phosphoryl ester exchange and N→O migration reactions of dimethyloxyphosphoryl-threonin" Chem.Letters. 3-4 (1997)
[文献書誌] H.WATANABE and S.IWATA: "Molecular orbital studies of the structures and reactions of a singly charged calcium ion with water clusters. Ca^+(H_2O)_n" J.Phys.Chem.A101. 487-496 (1997)
[文献書誌] C.-G.ZHAN and S.IWATA: "Ab initio studies on the structures,vertical electron detachment energies and fragmentation energies of C_nB^- clusters" J.Chem.Phys.A101. 591-596 (1997)
[文献書誌] X.ZHAO, H.IMAHORI, C.-G.ZHAN, Y.SAKATA, S.IWATA: "Resonance Raman and FTIR spectra of isotope-labeled reduced 1,4-benzoquinone and its protonated forms in solution" J.Phys.Chem.A101. 591-596 (1997)
[文献書誌] Y.M.LI and S.IWATA: "Theoretical studies of cyclic isomers of HNO_x(x=2-6)" Bull.Chem.Soc.Jpn,. 70. 79-88 (1997)
[文献書誌] F.R.ORNLLAS, L.T.UENO and S.IWATA: "Diazasilene (SiNN): Is there a conflict between experiment and theory?" J.Phys.Chem.106. 151-157 (1997)
[文献書誌] J.HRUSAK and S.IWATA: "The vibrational spectrum of H_2O_2^+ radical cation : An illustration of symmetry" J.Chem.Phys.106. 4877-4888 (1997)
[文献書誌] J.HRUSAK, S.TEN-NO and S.IWATA: "Quadratic Configuration Interaction versus Coupled Cluster Theory : Importance of Orbital Relaxation Phenomena in CuH and CuF" J.Phys.Chem.106. 7185-7192 (1997)
[文献書誌] J.HRUSAK, D.SCHRODER, H.SCHWARZ and S.IWATA: "Comparative ab initio and hybrid DFT studies relevant to an experimental investigation of neutral and cationic [Si,P,H_2] isomers" Bull.Chem.Soc.Jpn.70. 777-787 (1997)
[文献書誌] J.HRUSAK, D.SCHRODER and S.IWATA: "The ground state (^1A_1) and the lowest (^3B_2) of the phenyl C_6H_5^+ forms in solution" J.Phys.Chem.106. 7541-7549 (1997)
[文献書誌] J.K.PARK and S.IWATA: "Ab initio study of photchemical reactions of ammonia dimer systemsmode-mode coupling in liquid molecules" J.Phys.Chem. A101. 3613-3618 (1997)
[文献書誌] T.TSUKUDA, M.SAEKI, S.IWATA and T.NAGATA: "Reaction of negatively-charged clusters of carbon dioxide with CH_3I : Formation of novel molecular anion CH_3CO_2I" J.Phys.Chem. A101. 5103-5110 (1997)
[文献書誌] Y.M.LI and S.IWATA: "Theoretical study of cyclic radicals NO_x(x=2-6)" Chem.Phys.219. 209-219 (1997)
[文献書誌] Y.M.LI and S.IWATA: "Potential energy surfaces of the ground and low-lying states of HCCS and NCS : CASSCF,MRCI and CCSD(T) studies" Chem.Phys.Letters. 273. 91-97 (1997)
[文献書誌] Reiko Kishi, Suehiro Iwata, Atsushi Nakajima and Koji Kaya: "Geometric and electronic structures of silicon-sodium binary clusters. I.Ionization energy of Si_nNa_m" J.Chem.Phys.170. 3056-3070 (1997)
[文献書誌] M.GOMEI, R.KISHI, A.NAKAJIMA, S.IWATA and K.KAYA: "Ab initio MO studies of neutral and anionic SiC_n clusters (n=2-5)" J.Chem.Phys.107. 10051-10061 (1997)
[文献書誌] W.N.WANG, K.N.FAN and S.IWATA: "Ab initio MO studies of Si_4NO^+ cluster" Chem.Phys.Letters. 273. 337-344 (1997)
[文献書誌] F.ORNELLAS and S.IWATA: "Ab initio study of the isomers : HNNSi,HSiNN,and HNSiN" Bull.Chem.Soc.Jpn. 70. 2057-2062 (1997)
[文献書誌] H.WATANABE, T.ASADA and S.IWATA: "Theoretical prediction of inttracluster reactions of B^+(H_2O)_2 and B^+(H_2O)_3 : Hybrid procedure of ab initio MO calculations and Monte Carlo samplings." Bull.Chem.Soc.Jpn,. 70. 2619-2629 (1997)
[文献書誌] F.R.ORNELLAS and S.IWATA: "A theoretical study of the electronic structure and spectroscopic properties of the low-lying electronic states of the molecule SiB" J.Phys.Chem.107. 6782-6794 (1997)
[文献書誌] S.KRISHNMURTY, R.K.ROY, R.VERTRIVEL, S.IWATA, S.PAL: "Local hard-soft acid base principle : a critical study" J.Chem.Phys.101. 7253-7257 (1997)
[文献書誌] C.-G.ZHAN and S.WATA: "Ab initio studies on the structures,vertical electron detachment energies and stabilities of C_nP^-" J.Chem.Phys.107. 7323-7330 (1997)
[文献書誌] A.FIEDLER and S.IWATA: "Density functional crystal orbital study on the normal vibrations of polyacetylenes and polymethyineimine" J.Chem.Phys.107. 10075-10084 (1997)
[文献書誌] M.SAEKI L.i ZHU, T.TSUKUDA, S.IWATA, and T.NAGATA: "Photoabsorption and photofragmentation studies of acetyloxy iodide anion CH_3CO_2I^-" Chem.Phys.Letters. 280. 348-352 (1997)
[文献書誌] T.KODAMA, K.MOGI, M.AOYAGI, and T.KATO: "ESR Measurments of C_<60> anion crystals" Mol.Phys.Report.18. 121 (1997)
[文献書誌] S.KONDO, K.TOKUHASHI, and M.AOYAGI: "Ab Initio Energetic Calculations of Elementary Reactions Relevant to Low-Temperature Silane Oxidation" J.Phys.Chem.A101. 6015-6022 (1997)
[文献書誌] S.NANBU, S.MINAMINO, and M.AOYAGI: "Theoretical Study of the Potential Energy Surfaces and Dynamics of CaNC/CaCN" J.Chem.Phys.106. 8073-8083 (1997)
[文献書誌] R.KISHI, H.KAWAMATA, Y.I NEGISHI, S.IWATA, A.NAKAJIMA, K.KAYA: "Geometric and electronic structures of silicon-sodium binary clusters.II. Photoelectron spectroscopy of Si_nNa_m^- cluster anions" J.Chem.Phys.107. 10029-10043 (1997)
[文献書誌] A.FIEDLER and S.IWATA: "Portrait of diatomic FeN.A theoretical study" Chem.Phys.Letters. 271. 143-151 (1997)

1997 年度 実績報告書

並列計算による分子クラスターの分光学と化学反応の研究

研究代表者

岩田 末廣 岡崎国立共同研究機構, 分子科学研究所, 教授 (20087505)

研究成果

[文献書誌] C.-G.ZHAN and S.IWATA: "Theoretical prediction of the ^<31>P NMR chemical shift of the hexa-coordinate phosphorus intermediate for the phosphoryl ester exchange and N→O migration reactions of dimethyloxyphosphoryl-threonin" Chem.Letters. 3-4 (1997)

[文献書誌] H.WATANABE and S.IWATA: "Molecular orbital studies of the structures and reactions of a singly charged calcium ion with water clusters. Ca^+(H_2O)_n" J.Phys.Chem.A101. 487-496 (1997)

[文献書誌] C.-G.ZHAN and S.IWATA: "Ab initio studies on the structures,vertical electron detachment energies and fragmentation energies of C_nB^- clusters" J.Chem.Phys.A101. 591-596 (1997)

[文献書誌] X.ZHAO, H.IMAHORI, C.-G.ZHAN, Y.SAKATA, S.IWATA: "Resonance Raman and FTIR spectra of isotope-labeled reduced 1,4-benzoquinone and its protonated forms in solution" J.Phys.Chem.A101. 591-596 (1997)

[文献書誌] Y.M.LI and S.IWATA: "Theoretical studies of cyclic isomers of HNO_x(x=2-6)" Bull.Chem.Soc.Jpn,. 70. 79-88 (1997)

[文献書誌] F.R.ORNLLAS, L.T.UENO and S.IWATA: "Diazasilene (SiNN): Is there a conflict between experiment and theory?" J.Phys.Chem.106. 151-157 (1997)

[文献書誌] J.HRUSAK and S.IWATA: "The vibrational spectrum of H_2O_2^+ radical cation : An illustration of symmetry" J.Chem.Phys.106. 4877-4888 (1997)

[文献書誌] J.HRUSAK, S.TEN-NO and S.IWATA: "Quadratic Configuration Interaction versus Coupled Cluster Theory : Importance of Orbital Relaxation Phenomena in CuH and CuF" J.Phys.Chem.106. 7185-7192 (1997)

[文献書誌] J.HRUSAK, D.SCHRODER, H.SCHWARZ and S.IWATA: "Comparative ab initio and hybrid DFT studies relevant to an experimental investigation of neutral and cationic [Si,P,H_2] isomers" Bull.Chem.Soc.Jpn.70. 777-787 (1997)

[文献書誌] J.HRUSAK, D.SCHRODER and S.IWATA: "The ground state (^1A_1) and the lowest (^3B_2) of the phenyl C_6H_5^+ forms in solution" J.Phys.Chem.106. 7541-7549 (1997)

[文献書誌] J.K.PARK and S.IWATA: "Ab initio study of photchemical reactions of ammonia dimer systemsmode-mode coupling in liquid molecules" J.Phys.Chem. A101. 3613-3618 (1997)

[文献書誌] T.TSUKUDA, M.SAEKI, S.IWATA and T.NAGATA: "Reaction of negatively-charged clusters of carbon dioxide with CH_3I : Formation of novel molecular anion CH_3CO_2I" J.Phys.Chem. A101. 5103-5110 (1997)

[文献書誌] Y.M.LI and S.IWATA: "Theoretical study of cyclic radicals NO_x(x=2-6)" Chem.Phys.219. 209-219 (1997)

[文献書誌] Y.M.LI and S.IWATA: "Potential energy surfaces of the ground and low-lying states of HCCS and NCS : CASSCF,MRCI and CCSD(T) studies" Chem.Phys.Letters. 273. 91-97 (1997)

[文献書誌] Reiko Kishi, Suehiro Iwata, Atsushi Nakajima and Koji Kaya: "Geometric and electronic structures of silicon-sodium binary clusters. I.Ionization energy of Si_nNa_m" J.Chem.Phys.170. 3056-3070 (1997)

[文献書誌] M.GOMEI, R.KISHI, A.NAKAJIMA, S.IWATA and K.KAYA: "Ab initio MO studies of neutral and anionic SiC_n clusters (n=2-5)" J.Chem.Phys.107. 10051-10061 (1997)

[文献書誌] W.N.WANG, K.N.FAN and S.IWATA: "Ab initio MO studies of Si_4NO^+ cluster" Chem.Phys.Letters. 273. 337-344 (1997)

[文献書誌] F.ORNELLAS and S.IWATA: "Ab initio study of the isomers : HNNSi,HSiNN,and HNSiN" Bull.Chem.Soc.Jpn. 70. 2057-2062 (1997)

[文献書誌] H.WATANABE, T.ASADA and S.IWATA: "Theoretical prediction of inttracluster reactions of B^+(H_2O)_2 and B^+(H_2O)_3 : Hybrid procedure of ab initio MO calculations and Monte Carlo samplings." Bull.Chem.Soc.Jpn,. 70. 2619-2629 (1997)

[文献書誌] F.R.ORNELLAS and S.IWATA: "A theoretical study of the electronic structure and spectroscopic properties of the low-lying electronic states of the molecule SiB" J.Phys.Chem.107. 6782-6794 (1997)

[文献書誌] S.KRISHNMURTY, R.K.ROY, R.VERTRIVEL, S.IWATA, S.PAL: "Local hard-soft acid base principle : a critical study" J.Chem.Phys.101. 7253-7257 (1997)

[文献書誌] C.-G.ZHAN and S.WATA: "Ab initio studies on the structures,vertical electron detachment energies and stabilities of C_nP^-" J.Chem.Phys.107. 7323-7330 (1997)

[文献書誌] A.FIEDLER and S.IWATA: "Density functional crystal orbital study on the normal vibrations of polyacetylenes and polymethyineimine" J.Chem.Phys.107. 10075-10084 (1997)

[文献書誌] M.SAEKI L.i ZHU, T.TSUKUDA, S.IWATA, and T.NAGATA: "Photoabsorption and photofragmentation studies of acetyloxy iodide anion CH_3CO_2I^-" Chem.Phys.Letters. 280. 348-352 (1997)

[文献書誌] T.KODAMA, K.MOGI, M.AOYAGI, and T.KATO: "ESR Measurments of C_<60> anion crystals" Mol.Phys.Report.18. 121 (1997)

[文献書誌] S.KONDO, K.TOKUHASHI, and M.AOYAGI: "Ab Initio Energetic Calculations of Elementary Reactions Relevant to Low-Temperature Silane Oxidation" J.Phys.Chem.A101. 6015-6022 (1997)

[文献書誌] S.NANBU, S.MINAMINO, and M.AOYAGI: "Theoretical Study of the Potential Energy Surfaces and Dynamics of CaNC/CaCN" J.Chem.Phys.106. 8073-8083 (1997)

[文献書誌] R.KISHI, H.KAWAMATA, Y.I NEGISHI, S.IWATA, A.NAKAJIMA, K.KAYA: "Geometric and electronic structures of silicon-sodium binary clusters.II. Photoelectron spectroscopy of Si_nNa_m^- cluster anions" J.Chem.Phys.107. 10029-10043 (1997)

[文献書誌] A.FIEDLER and S.IWATA: "Portrait of diatomic FeN.A theoretical study" Chem.Phys.Letters. 271. 143-151 (1997)

1997 年度実績報告書

岩田末廣岡崎国立共同研究機構, 分子科学研究所, 教授 (20087505)