2P126    ෆẆ㟁Ꮚ㐣⛬ࡢ⌮ㄽ⢭ᐦศග㸦ศᏊ◊ 1㸪⥲◊኱ 2㸪QCRI3㸧‫ۑ‬Ụཎ ṇ༤ 1, 2㸪୰㎷ ༤ 3ᗎ ෆẆ㟁Ꮚ㐣⛬䛾⌮ㄽ◊✲䛷䛿䚸㌶㐨⦆࿴䛸㟁Ꮚ┦㛵䜢䛸䜒䛻⢭ᗘ䜘䛟グ㏙䛩䜛䛣䛸䛜㔜せ䛷䛒䜛䚹ᡃ䚻䛿䚸SAC-CI general-R ἲ[1]䜢⏝䛔䛶䚸ᵝ䚻䛺ෆẆ㟁Ꮚ㐣⛬䠄ෆẆບ㉳䞉䜲䜸䞁໬≧ែ䚸ෆẆ䜲䜸䞁໬䝃䝔䝷䜲䝖≧ែ䚸᣺ື䝇䝨䜽䝖䝹䠅䜢◊✲䛧䛶䛝䛯[2]䚹ᮏⓎ⾲䛷䛿䚸ศᏊሙศ⿣䜔䝇䝢䞁㌶
㐨ศ⿣䛻ᇶ䛵䛟」㞧䛺ෆẆບ㉳䝇䝨䜽䝖䝹䛾ゎᯒ䚸➨୕࿘ᮇඖ⣲䛾ෆẆ㟁Ꮚ㐣⛬䛻䛚䛡䜛┦ᑐㄽⓗຠᯝ[3]䚸䝞䝺䞁䝇䞉䝸䝗䝧䝹䜾┦஫స⏝䛸䛭䛾ᗘຠᯝ[4]䛻䛴䛔䛶ሗ࿌䛩䜛䚹᪉ἲ SO2 䛾 2p ෆẆບ㉳≧ែ䜢 SAC-CI general-R ἲ䛻ᇶ䛵䛔䛶◊✲䛧䛯䚹䝇䝢䞁㌶㐨┦஫స⏝䜢
SAC-CI ゎ䛻䛴䛔䛶ホ౯䛧䚸䝫䝔䞁䝅䝱䝹᭤㠃䛛䜙᣺ື䝇䝨䜽䝖䝹䜢ィ⟬䛧䛯䚹┦ᑐㄽⓗຠᯝ䛾◊✲䛷䛿䚸➨୕࿘ᮇ䛾ཎᏊ(Si, P, S, Cl)䜢ྵ䜐ศᏊ䛾ෆẆ䜲䜸䞁໬≧ែ䛾⌮ㄽィ⟬䜢⾜䛳䛯䚹DouglassKroll-Hess(DK2)䝝䝭䝹䝖䝙䜰䞁䛾 spin-free 㒊ศ䜢⪃៖䛧䚸SAC-CI SDT-R ἲ䜢⏝䛔䛶ィ⟬䛧䛯䚹䜎䛯䚸
N2O 䛾ບ㉳≧ែ䛿 Equivalent-core model 䜢⏝䛔䛶 direct SAC-CI ἲ䜢⏝䛔䛯䚹⤖ᯝ㻌
䠍䠊SO2 䛾 S2p-!*ෆẆບ㉳≧ែ
SO2 䛾 S2p-"!*ບ㉳≧ែ䛻䛿ศᏊሙศ⿣䚸䝇䝢䞁㌶㐨ศ⿣䚸᣺ືᵓ㐀䛜䛒䜚䚸」㞧䛺䝇䝨䜽䝖䝹䜢♧䛩䚹⌮ㄽィ⟬䛛䜙ᑐ⛠ఙ⦰᣺ື᪉ྥ䛻ᵓ㐀ኚ໬䛜኱䛝䛟䚸᣺ືᵓ㐀䛿୺䛻ᑐ⛠ఙ⦰䛻䜘䜛䜒䛾䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䚹ᅗ 1 䛿䚸ᑐ⛠ᛶ䜢ศ㞳䛧䛯䝇䝨䜽䝖䝹(B1 䛾䜏)䛸⌮ㄽ䝇䝨䜽䝖䝹䜢ẚ㍑䛧䛯䜒䛾䛷䛒䜛䚹⌮ㄽ䛿ᐇ㦂䜢䜘䛟ㄝ᫂䛧䛶䛚䜚䚸௒ᚋ䚸3 ḟඖ䛾᣺ື䝰䞊䝗䛻㛵䛩䜛ヲ⣽䛺ゎᯒ䜢⾜䛖䚹䠎䠊➨୕࿘ᮇඖ⣲䜢ྵ䜐ศᏊ䛾ෆẆ䜲䜸䞁໬䜶䝛䝹䜼䞊➨୕࿘ᮇඖ⣲䜢ྵ䜐ศᏊ䚸SiH4, PH3, H2S, OCS, CH3Cl 䛾ෆẆ䜲䜸䞁໬䜶䝛䝹䜼䞊䛻䛴䛔䛶᳨ウ䛧䛯(⾲ 1)䚹┦ᑐㄽⓗຠᯝ䛿 4䡚9 eV ⛬ᗘ䛒䜛䚹┦ᑐㄽⓗຠᯝ䛿䚸㌶㐨㏆ఝ䛸㟁Ꮚ┦㛵䜢⪃៖䛧䛯ሙྜ䛷 0.15䡚0.4 eV ⛬ᗘ䛾㐪䛔䛜䛒䜚䚸┦ᑐㄽⓗຠᯝ䛸㟁Ꮚ┦㛵䛾ຠᯝ䛜┦ẅ䛩䜛䛣䛸䛜♧䛥䜜䛯䚹㻿㻻㻞㻌 㻌㻿㻞㼜㻙!㻖㻌㻔㻮㻝㻕㻌㼄㻼㻿㻌㻳㼑㼚㼑㼞㼍㼘㻙㻾㻌ᅗ 㻝㻚㻌 㻿㻻㻞 䛾 㻿㻞㼜㻙!㻖ບ㉳≧ែ㻔㻮㻝㻕䛾㼄㻼㻿 䛸 㻿㻭㻯㻙㻯㻵㻌㼓㼑㼚㼑㼞㼍㼘㻙㻾 ἲ䛾ẚ㍑㻌

⾲ 1. SiH4, PH3, H2S, OCS, CH3Cl ࡢෆẆ࢖࢜ࣥ໬࢚ࢿࣝࢠ࣮(eV)ศᏊᐇ㦂┦ᑐㄽⓗ 㠀┦ᑐㄽⓗ ┦ᑐㄽⓗຠᯝ (eV)SAC-CI
SAC-CI
SAC-CISCF

SiH41847.1

1848.24

1843.96

4.28

3.97

PH3

2150.52151.252146.32

4.93

5.30

H2S

2478.52479.512472.98

6.53

6.94

OCS

2480.32481.842475.06

6.78

6.93

CH3Cl

2829.42832.152823.358.808.95䠏䠊䝞䝺䞁䝇䞉䝸䝗䝧䝹䜾ΰྜ䛸䛭䛾 ᗘຠᯝศᏊ䛿ෆẆ㟁Ꮚ㐣⛬䛻䛚䛔䛶≉ᚩⓗ䛺ᵓ㐀ኚ໬䜢♧䛩䚹ゅᗘศゎ䜲䜸䞁཰㔞ศගἲ㻔㻭㻾㻵㼅㻕䛷䛿䚸✵㛫ᑐ⛠ᛶ䜢ศ㞳䛧䛯᣺ື䝇䝨䜽䝖䝹䛾ほ䛻ᡂຌ䛧䛶䛔䜛䚹ᮏ◊✲䛷䛿䚸㻺㻞㻻 ศᏊ䛾 㻻㻝㼟 ෆẆບ㉳䛻క䛖ᵓ㐀ኚ໬䛸䝞䝺䞁䝇䞉䝸䝗䝧䝹䜾┦஫స⏝䛻䛴䛔䛶᳨ウ䛧䛯䚹㻌㻺㻞㻻㻌 䛾 㻻㻝㼟 ෆẆບ㉳≧ែ䛾≉ᚩⓗ䛺ᵓ㐀ኚ໬䛸᣺ື䝇䝨䜽䝖䝹㻌 ᅗ 㻞 䛻 㻺㻞㻻 䛾 㻻㻝㼟 ෆẆບ㉳䛾ᐇ㦂䝇䝨䜽䝖䝹䜢♧䛩䚹ᅗ䛿 㻟㻜㻜㻷 䛸 㻣㻜㻜㻷 䛷ほ䛥䜜䛯䝇䝨䜽䝖䝹䜢䚸䝪䝹䝒䝬䞁ศᕸ䛛䜙ጞ≧ែ䛜᣺ືᇶᗏ≧ែ䛸᣺ືບ㉳≧ែ䛻ศ㞳䛧䛯䜒䛾䛷䛒䜛䚹≉䛻 㻠㼟#≧ែ䛷䛿㧗᣺ື≧ែ䛜ບ㉳䛥䜜䛯᣺ື䝇䝨䜽䝖䝹䛜ほ䛥䜜䛶䛔䜛䚹ᅗ 㻟 䛻䞉ᑐ⛠ᛶ䛾ບ㉳≧ែ䛾 㻺㻻 ㊥㞳䛻ᑐ䛩䜛䝫䝔䞁䝅䝱䝹᭤⥺䜢♧䛩䚹㻠㼟#≧ែ䛿ᵓ㐀ኚ໬䛜኱䛝䛟䚸㻻㻝㼟 ບ㉳䛻䜘䛳䛶㧗᣺ື≧ែ䛜ບ㉳䛥䜜䜛䚹䛣䜜䛿 㻠㼟#≧ែ䛻䛚䛔䛶䝞䝺䞁䝇䞉䝸䝗䝧䝹䜾ΰྜ䛜䛚䛝䛶䛔䜛䛣䛸䛻䜘䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㻌ጞ≧ែ䛾᣺ືບ㉳䛾ຠᯝ㻌 䛥䜙䛻ጞ≧ែ䛾᣺ືບ㉳䛾ຠᯝ䛻䛴䛔䛶᳨ウ䛧䛯䚹ᐇ㦂䝇䝨䜽䝖䝹䛷䛿䚸!㻖ບ㉳䛿ጞ≧ែ䛜ኚゅ᣺ືບ㉳≧ែ䛾䛸䛝䚸᣺ືᇶᗏ≧ែ䛸ẚ䜉䛶ᖜ䛜ᣑ䛜䜚䚸ప䜶䝛䝹䜼䞊ഃ䛻䝅䝣䝖䛧䛶䛔䜛䚹䜎䛯䚸㻟㼟#㻌 㻘㻌 㻠㼟#䝸䝗䝧䝹䜾≧ែ䛷䛿྾཰ᙉᗘ䛜᣺ືᇶᗏ≧ែ䛾䜒䛾䛸ẚ䜉䛶ᙉᗘ䛜ᑠ䛥䛟䛺䜛䚹䛣䜜䜙䛾ෆẆບ㉳䝇䝨䜽䝖䝹䛾ጞ≧ែ౫Ꮡᛶ䛻䛴䛔䛶䚸ᒅ᭤ᵓ㐀䛻䛚䛡䜛䝫䝔䞁䝅䝱䝹᭤⥺䛸㟁Ꮚᐦᗘ䛾ᗈ䛜䜚㻔ᅗ 㻠㻕䛛䜙᫂䜙䛛䛻䛧䛯䚹㻌


0.1

bent
A' (!*)A' (4p!)㻿㼑㼏㼛㼚㼐㻌㼙㼛㼙㼑㼚㼠㻘㻌㻨㼞㻞㻪㻌㻔㼍㼡㻕

Intensity (arb. units)

0.2(0,0,0)(0,$2,0)

3s#*

0.0

(b) I(90)linearA'' (!*)

0.2

0.1

㻠㻜㻜

O1s
4s# 3d 5s 6s(a) I(0)bent
A' (!*)(0,0,0)(0,$2,0)

3p! 3d 4p

O1s

534

536
538
540
Photon energy (eV)A' (3p#)A' (3p!)2A' (3s#*)%%

1A" (! ) 1A' (! )㻝㻟㻡 㻝㻠㻜 㻝㻠㻡 㻝㻡㻜 㻝㻡㻡 㻝㻢㻜 㻝㻢㻡 㻝㻣㻜 㻝㻣㻡 㻝㻤㻜㻺㻺㻻㻌㼍㼚㼓㼘㼑㻌㻔㼐㼑㼓㼞㼑㼑㼟㻕542ᅗ 㻞㻚㻌㻺㻞㻻㻘㻌㻻㻝㼟 ෆẆບ㉳䝇䝨䜽䝖䝹㻌NNO
O1s excited statesA' (4s#)㻞㻜㻜㻝㻜㻜

0.0532A' (5s#)㻟㻜㻜ᅗ 㻟㻚㻌 㻺㻞㻻㻘㻌 㻻㻝㼟 ෆẆບ㉳≧ែ䛾䝫䝔䞁䝅䝱䝹᭤㠃䠖㻺㻻 ㊥㞳᪉ྥ䛾䜹䝑䝖㻌ᅗ 㻠㻚㻌㻺㻞㻻㻘㻌㻻㻝㼟 ෆẆບ㉳≧ែ䛾⤖ྜゅ᪉ྥ䛾㟁Ꮚᐦᗘ䛾ᗈ䛜䜚㻌

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