2P041

㻃 㻃 㻃 㻃 ┞ᑊㄵⓏ䝦䝋䝯හṾ䝡䝊䝷䜻䝧䝯䟺MCP䟻Ἢ䛱䜎䜑㻃 㻃 㻃 䜯䝯䜷䜶䝷䜳䝭䜽䝃䞀䛴㞹Ꮔᵋ㏸䛱㛭䛟䜑⌦ㄵⓏ◂✪(ஐኬ㝌⥪⌦ᕝ1㸡CREST2)䕵ኬሔ ᗀ᪺1䟾ᓙ 㞖⣎1䟾᲻ ᐰᨼ1䟾୔ይỄష1,2

i.ᗆ࣬┘Ⓩ ࿔᭿ᚂ⾪ࡡ VI ᪐࡞ࡢ㸡㍇࠷ࡵࡡ࠾ࡼ㡨࡞ O, S, Se, Te ࠿ᒌࡊ࡙࠽ࡽ㸡࢜ࣜࢤࢣࣤ᪐࡛⥪⛘ࡈࡿࡾ㸣㉰㡚㏷ࢩ࢘ࢴࢹἪ࡞ࡻࡽẴ┞୯࡞⏍ᠺࡊࡒ࢜ࣜࢤࢣࣤࢻࢿࢠࣚࢪࢰ࣭ࡡฦකᏕⓏ◂✪࡚ࡢ㸡S, Se,Te ࡡ㨩Ἢᩐ࠿ࡐࡿࡑࡿ㸡8࣬5-7࣬2 ࡛㸡ཋᏄ␊ྒࡡቌኬ࡞ఔ࠷΅ᑛࡌࡾᵕᏄ࠿ふῼࡈࡿ࡙࠽ࡽ [1-6]㸡࢜ࣜࢤࢣࣤࢠࣚࢪࢰ࣭ࡡ♟ࡌኣᙤ࡝ᵋ㏸࣬ᛮ㈻ࡢ⌦ᏕⓏふⅤ࠾ࡼ⮾࿝῕࠷㸣々㞟࡝࢜ࣜࢤࢣࣤࡡ໩Ꮥࢅ⌦よࡌࡾ࡞ࡢ㸡ᐁ㥺Ⓩ࢓ࣈ࣭ࣞࢲ࡞ຊ࠻㸡ḿࡊࡂ㞹Ꮔ┞㛭࡛┞ᑊㄵຝᯕࢅ⩻៎ࡊࡒฦᏄ㌮㐠ゝ⟤࡞ࡻࡾ⌦ㄵⓏ࢓
ࣈ࣭ࣞࢲ࠿ᚪさ࡚࠵ࡾ㸣ᮇ◂✪࡚ࡢ㸡᭩㎾ᠻࠍ࠿ GAMESS [7] ୕࡚Ᏸᠺࡊࡒ┞ᑊㄵⓏ࣓ࢸࣜහṾ࣎ࢷࣤࢨࣔࣜ㸝MCP㸞࡞ࡻࡾฦᏄᵋ㏸᭩㐲໩ࣈࣞࢡ࣑ࣚ [8] ࢅ ab initio ฦᏄ㌮㐠Ἢ㸝MP2㸞࡛㏻ິࡊ㸡࢜ࣜࢤࢣࣤࢠࣚࢪࢰ࣭ࡡᖼరᵋ㏸࣬㞹Ꮔᵋ㏸࡛྘ࠍࡡ㨩Ἢᩐ࡛ࡡ㛭౿ࢅ⌦ㄵⓏふⅤ࠾ࡼ᥀ࡖࡒ㸣ᅒ 1 ࢜ࣜࢤࢣࣤࢠࣚࢪࢰ࣭ࡡ㈻㔖ࢪ࣋ࢠࢹࣜ㸣㸝ᕞ㸞ᑚࡈ࠷ࢠࣚࢪࢰ࣭㸝ྎ㸞ኬࡀ࠷ࢠࣚࢪࢰ࣭
S, Se, Te ࡡ㨩Ἢᩐ࠿ࡐࡿࡑࡿ㸡8, 5-7, 2 ࡚࠵ࡾࡆ࡛࠿♟ࡈࡿ࡙࠷ࡾ㸣ᩝ⊡ [1-6] ࡻࡽ㸣iゝ⟤᪁Ἢ 㔔ඔ⣪ࢅྱࢆࡓ ab initio ฦᏄ㌮㐠ゝ⟤࡚ࡢ㸡ゝ⟤ㇿⲬࢅ΅ࡼࡌࡒࡴ㸡ୌ⯙࡞㸡᭯ຝහṾ࣎ࢷࣤࢨࣔࣜ㸝ECP㸞࠿౐ࢂࡿࡾ㸣ࡓ࠿㸡ECP Ἢ࡚ࡢ㸡౮㞹Ꮔ㌮㐠ࡡ⟿ᵋ㏸ࢅḿࡊࡂ්⌟࡚ࡀࡍ㞹Ꮔ┞㛭࠿㐛ኬフ౮ࡈࡿࡾࡒࡴ㸡⢥ᐠ࡝ฦᏄ∸ᛮೋࡡぜ✒ࡵࡽ࡞୘Ꮽ࠿ṟࡾ㸣ࡐࡆ࡚ᮇ◂✪࡚ࡢ㸡౮㞹Ꮔ㌮㐠ࡡḿࡊ࠷⟿ᵋ㏸ࢅ්⌟ࡊ㸡ࡻࡽ⢥ᐠ࡞ฦᏄ∸ᛮೋࢅゝ⟤࡚ࡀࡾ࣓ࢸࣜහṾ࣎ࢷࣤࢨࣔࣜ㸝2(5㸞Ἢࢅ㐲⏕ࡊ㸡㞹Ꮔ┞㛭࣬┞ᑊㄵຝᯕࢅྜྷ᫤࡞ཱིࡽ᡽ࡖࡒ ab initio ゝ⟤㸝MP2㸞࡞ࡻࡾᵋ㏸᭩㐲໩࣬ᣲິᩐよᯊࢅᐁ⾔ࡊࡒ㸣MP2 ゝ⟤୯࡚ࡢ㸡࢜ࣜࢤࢣࣤ㸝S, Se, Te㸞ୌཋᏄᙔࡒࡽ 6 ಴ࡡ౮㞹Ꮔ (ns)2(np)4 ࢅ┞㛭ࡈࡎࡒ㸣┞ᑊㄵⓏMCP ࢅ౐⏕ࡌࡾࡆ࡛࡞ࡻࡽ㸡㸝ࢪࣅࣤ㌮㐠Ѹ ┞பష⏕ࢅ㝎ࡂ㸞┞ᑊㄵຝᯕࢅ⩻៎࡞ྱࡴࡒ㸣 ┞ᑊㄵⓏ MCP ࡡࣂࣆ࢚࣭࣏ࣤࢪ࣬⢥ᗐࢅ☔ヾࡌࡾࡒࡴ㸡MCP-xzp (x = d,t) [9]࣬Dunning-AE : cc-pVXZ (X= D, T) [10]㸡Peterson-ECP : cc-pVXZ-PP (X = D, T) [11]㸡୔⛸㢦ࡡ correlation consistent ᇱᗇࢅ⏕࠷ࡒ MP2 ┞㛭࢙ࢾ࣭ࣜ࢟ࡡゝ⟤⤎ᯕࢅẒ㍉᳠ゞࡊࡒ㸣ᮇ◂✪࡚⏕࠷ࡒ S, Se, Te ࡞ᑊࡌࡾᇱᗇ㛭ᩐࡡࢦ࢕ࢫࡢ㸡⾪ 1 ࡞♟ࡊࡒ㏳ࡽ࡚࠵ࡾ㸣MCP-tzp ࡡ⢥ᗐࢅ㸡ᑚࢦ࢕ࢫࢠࣚࢪࢰ࣭ Xn (X = S, Se, Te; n = 1-4) ࡞ࡗ࠷࡙☔࠾ࡴࡒᚃ㸡
MP2/MCP-tzp ࣝ࣊ࣜࡡ ab initio ゝ⟤ࢅ Xn (X = S, Se, Te; n = 5-8) ࡱ࡚ࡡ୯ࢦ࢕ࢫࢠࣚࢪࢰ࣭࡞㐲⏕ࡊ㸡ࢠࣚࢪࢰ࣭ࡡᏭᏽᵋ㏸㸝␏ᛮమ㸞࣬ฆ㞗࢙ࢾ࣭ࣜ࢟࣬㞹Ꮔᵋ㏸࡞ࡗ࠷࡙ࡡ᝗ሒࢅᚋࡒ㸣 ධ࡙ࡡゝ⟤࡞࠽࠷࡙㸡ࣈࣞࢡ࣑ࣚࡢ GAMESS [7] ࢅ౐⏕ࡊࡒ㸣⾪ 1 Correlation consistent DZP level ᇱᗇ㛭ᩐࡡ⛸㢦㸝MCP࣬AE࣬ECP㸞࡛ࡐࡿࡼࡡࢦ࢕ࢫ
ඔ⣪

Miyoshi-MCP : MCP-dzp a)

Dunning-AE : cc-pVDZ b)Peterson-ECP : cc-pVDZ-PP c)S[4s4p3d]/(2s2p1d)[12s8p1d]/(4s3p1d)-Se[7s6p7d]/(3s3p2d)[14s11p6d]/(5s4p2d)[8s7p7d]/(4s3p2d)Te[8s7p8d]/(3s3p2d)-[8s6p6d]/(4s3p2d)a) Ref. [9], b) Ref. [10], c) Ref. [11] ͤ TZP level ᇱᗇ࡚ࡡゝ⟤ࡵᐁ⾔ࡊ࡙࠷ࡾ㸣i⤎ᯕ࡛⩻ᐳ ᅒ 2 ࡞ Se2ࠤSe4 ࡱ࡚ࡡᏭᏽᵋ㏸࡛㸡ᅒ 3 ࡞ࡐࡿࡼࡡ MP2 ┞㛭࢙ࢾ࣭ࣜ࢟ࢅ྘ᇱᗇ࡚Ẓ㍉ࡊࡒᲤࢡࣚ
ࣆࢅ♟ࡌ㸣S, Te ࡡሔྙ࡞ࡵྜྷᵕ࡝ࢠࣚࢪࢰ࣭ᵋ㏸ࢅぜࡗࡄࡾࡆ࡛࠿࡚ࡀࡒ㸣
2.218

2.2502.413(a) Se2
linear(b-1) Se3
triangle: +1.3

2.228
2.438(c-1) Se4
boat: +39.5(b-2) Se3
bent: ±0.0

2.449

2.928(c-2) Se4
rectangle: ±0.0(c-3) Se4
square: +45.7

ᅒ 2 Sen (n = 2-4) ࢠࣚࢪࢰ࣭ࡡᏭᏽᵋ㏸㸝Å㸞࡛   ␏ᛮమࡡ┞ᑊ࢙ࢾ࣭ࣜ࢟㸝kcal mol-1㸞
(୕ᅒ୯ࡡೋࡢ MP2/MCP-dzp ࡡࡵࡡ)Se1

Se2 (a)Se3 (b-1) (b-2)

Se4 (b-1) (b-2) (b-3)ᅒ 3 Sen (n = 1-4) ࢠࣚࢪࢰ࣭ࡡ྘Ꮽᏽᵋ㏸࡞
࠽ࡄࡾ MP2 ┞㛭࢙ࢾ࣭ࣜ࢟ ᅒ 3 ࡻࡽ㸡┞ᑊㄵⓏ MCP ࡡゝ⟤⤎ᯕࡢ㸡ධ㞹Ꮔゝ⟤: cc-pVDZ ࠽ࡻࡦ㸡small-core(SC) RECP:
cc-pVDZ-PP ࡡ⤎ᯕ࡛ࡻࡂୌ⮬ࡊ࡙࠷ࡾࡆ࡛࠿ฦ࠾ࡾ㸣ࡆࡆ࡚ኬ஥࡝ࡆ࡛ࡢ㸡ᚉᮮࡡ SC-RECP ࡛㸡ᠻࠍ
ࡡ┞ᑊㄵⓏ MCP ࡡ㐢࠷࡚࠵ࡾ㸣┞㛭࢙ࢾ࣭ࣜ࢟࡞ࡗ࠷࡙ධ㞹Ꮔゝ⟤࡛࡮࡯ྜྷᵕ࡝ࢠ࢛ࣛࢷ࢔ࡡ⤎ᯕࢅ୙࠻ࡾࡒࡴ࡞㸡 MCP-dzp ࡚ࡢ㸡᭯ຝ࣎ࢷࣤࢨࣔࣜ࡞⨠ࡀᥦ࠻ࡍ㟚࡞᡽ࡖ࡙࠷ࡾ㌮㐠㸡㸝࠽ࡻࡦࡐࡡ㞹Ꮔᩐ㸞࠿௙ࡡ᪁Ἢ࡛Ẓ࡬࡙᪺ࡼ࠾࡞ᑛ࡝࠷㸣ࡗࡱࡽ㸡┞ᑊㄵⓏ2(5Ἢ࡚ࡢ㸡ࠔᚉᮮࡡ7*(5࡞Ẓ࡬㸡ࡻࡽࢤࣤࣂࢠࢹ࡝ゝ⟤㔖࡚㸡ධ㞹Ꮔ┞ᑊㄵⓏฦᏄ㌮㐠ゝ⟤㸡࠵ࡾ࠷ࡢ8(7*(5ゝ⟤࡞༆ᩓࡌࡾ⤎ᯕࢅᚋࡾࡆ࡛࠿࡚ࡀࡾࠕ࡛࠷࠹ࡆ࡛࠿♟ࡈࡿ࡙࠷ࡾ㸣 5 㔖మ௧୕ࡡࢦ࢕ࢫࢅࡵࡖࡒࢠࣚࢪࢰ࣭࡞ࡗ࠷࡙ࡵྜྷᵕ࡞᭩㐲໩ゝ⟤ࢅ⾔ࡖࡒ㸣S, Se, Te ࢠࣚࢪࢰ࣭ࡡฆ㞗࢙ࢾ࣭ࣜ࢟ࡡࢦ࢕ࢫ౪Ꮛᛮ㸡㨩Ἢᩐ࡛ࡡ㛭ࢂࡽࡡレ⣵ࡢ㸡ᙔ᪝㸡レ⣵࡞ሒ࿈ࡌࡾ㸣࠘ཤ⩻ᩝ⊡࠙ [1] M. Yao et al., Sur. Rev. Lett. 3, 201 (1996). [2] K Nagaya et al., J. Non-Cryst. Solids, 205-207, 807(1996). [3] K Nagaya et al., Trans. Mat. Res. Soc., 20, 404 (1996). [4] T. P. Martin., J. Chem. Phys., 81, 4426(1984)., [5] A. Benamar et al., Z. Phys. D, 15, 237 (1991)., [6] J. Becker et al., Z. Phys. Chem, 173, 21 (1991)., [7]M. W. Schmidt et al., J. Comput. Chem. 14, 1347 (1993), [8] ฦᏄᵋ㏸⥪ྙゞㄵఌ 2006; ᲻ 2E05., [9] (a) E.
Miyoshi et al., J. Chem. Phys., 122, 074104 (2005).,(b) MCP ࢛ ࣤ ࣚ ࢕ ࣤ ࣚ ࢕ ࣇ ࣚ ࣛ ࣭ :http://meg.cube.kyushu-u.ac.jp/sapporo3/index.jsp [10] D. E. Woon and T. H. Dunning, J. Chem. Phys., 98, 1358 (1993).
[11] K.A. Peterson et al., J. Chem. Phys., 119, 11113 (2003).