SENAC Vol. 53, No. （2 2020. 4）― 1 ―［共同研究成果］

CO2,1,,1

1,,2,1

1,1,1,

1

1

12,.
.
,.

,,,surface hopping.
(CO2)2+,

CO2.

1.
2.

,.

,,.
1800

,
Born–Oppenheimer

.

,.

,,.

,

1.

,.

,,,.

.

1,,.
,

1927
1. Born[1], 5.
Oppenheimer
1932

Landau, Zener, Stückelberg2[2–24].
,,. Zhu–Nakamura

60

1992
Zhu
[5–8]. 12Zhu–Nakamura
5Nakamura1,

― 2 ―

SENAC Vol. 53, No. （2 2020. 4）

SENAC Vol. 52, No. 1,[9]

.

.
,.
,,.

,,.

,.
surface hopping[10],,.

,
Zhu–Nakamura
surface hopping[11].

,SENAC Vol. 52, No. 1
,
CO2

[9].

,
(CO2)2+.

2.
2.1

surface hopping
Preston,Tully

surface hopping[10] ,.

,,.

,,
1 .
fewest switches, Tully

Vj (R)
Schrödinger,[12]

Zhu–Nakamura. surface hopping[13–15]HOP
R(t),[16].

2.2

Ehrenfest

Meyer
mean field

MillerEhrenfest.

Schrödinger

STAY

Vi (R)R1

surface hopping

.

[17]
,

Vj (R)

,R(t)

2 .
.

,Vi (R)R,.

or2

Ehrenfest.

非断熱分子動力学法の分子会合体への適用：
CO2 二量体カチオンの光解離反応シミュレーション

― 3 ―

2.3
,
[18–20].
, Yonehara
Takatsukaphase-space averaging and natural,branching [18],eigenforce.
eigenforce.
,

Vj (R)
Rj(t)
R(t)
Ri(t)

Vi (R)

R
3 phase-space averaging and.
natural branching

3 .
,.

2.4
,

,. Kondorskiy

Nakamura

surface hopping

multiple cloning[21]. Shalashilin
Ehrenfest [22], Martinez
multiple spawning [23].
Ehrenfest
multiple spawning[24],.

2.5,NHartree

Rnni R1 , R2 ,nimn

Rn , tRn.

mn,Hartree. Meyeri(R1, R2, …, RN, t),t.

, RN , t

m1

m2

1mN

1N

ami1m2 mN t

n 1ni
mni

i

1,,i

[25]

10Rn , t(1)i, am1m2 mN t

.1
[26].

Hartree,[27–29].

3.

(CO2)2+1,Zhu–Nakamura
surface hopping(CO2)2,+.

,.

3.1,. Zhu–Nakamura.

― 4 ―

SENAC Vol. 53, No. （2 2020. 4）.
,. Zhu1[15].

Zhu–Nakamura,,.

,,.

Zhu
[9]

3.2

SENAC Vol. 52, No. 1.

(CO2)2+(CO2)2+(CO2)2+CO2+.

CO2C2h4,5[30,31].
. (CO2)2+,2

5[32,33]2.
,,.
. (CO2)2+,.

C2h
R = 3.5 Å

4= 37°(CO2)2+X.
SA-CASSCF(7,4)/cc-pVTZ.

5

CO2+.

[33]

.

(CO2)2+Molpro [34,35].
aug-cc-pVTZ
[36]
, 17
13
SA-CASSCF[37,38], C–CR6 .
4.
532 nm,X
3C.

/ eV3.32B Au

22X Bu6,
surface
hopping
Newton-X [39–41].

CC Ag,.

532 nm2A Bg(CO2)2+

C–C

R/Å

C–C

R.

CASSCF(17,13)/aug-cc-pVTZ.
.

SA[33]

非断熱分子動力学法の分子会合体への適用：
CO2 二量体カチオンの光解離反応シミュレーション

X

― 5 ―

4SA-CASSCF.
6
SA-CASSCF(17,13)/aug-cc-pVTZ
Wigner[42]
10,C, cc-pVTZ

[36]

7

44. X

, X

400 fs.

300.

t=0

C

0K.

,

3.4
7.
20 fs,
C,X

.
R

C–C

8.
,,.

9200 – 1500 m s 1.
, 1100 m s 1,5.

.

(b)

C–C

/%

R/Å(a)

7/ms 1/ fs
8

3.5

R. (b)

C–C

. (a)

9.

.

fewest switches
Tully

2.1,
fewest switches

1200 fs
fewestswitches

[33]

37

28

1953

120.
fewest switches, 6-31G
[36]

,%
93.

― 6 ―

SENAC Vol. 53, No. （2 2020. 4）. 200 fsR

C–C

7.0 Å.

4
1

2

200 fs. fewest switches,
52, fewest switches

.
10 %,

.
C12H10N2,,

fewest switches,.
.

2(CO2)2+
C–C,

R. 200 fs
6Å.
C–C–OR410R.

211. X

C–C

R > 3.5 Å,C,(,50 fs

4140°),

200 fs

73,X

86,.

8Å
9, C. X

.

,

R/Å

3.6

20 40 60 80 100 120 140 160 180

C–C–O

.
10C–C.

R/ degree
C–C–O

.

/ eV

R/Å

R/Å

3.7
3.6

X

C
C–C–O
11C–C

R

C–C

C–C

3.5
3.4
3.325

/ degree
C–C–O

24045
/ degree50
t=012.

SA-CASSCF(17,13)/cc-pVTZ.

3035
C–C–O

C–C

R

C–C–O

非断熱分子動力学法の分子会合体への適用：
CO2 二量体カチオンの光解離反応シミュレーション

t=0
1400 m s 1,

ms 1

― 7 ―R

12500.t=0

RR.

,2.

4.
(CO2)2+,.

, (CO2)2,+3

C

XX,

[33].

.
.

,.

,,,.
,,,,DNA.
,.

,NEC LX 406Re-2
L. Yue. Newton-X.
,C. ZhuJSPS,
JP16H04091

JP18K05022.

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