High Resolution Infrared Spectra of 11BF3 from
1650 cm-1 to 4300 cm-1
Tony Masiello, Thomas A. Blake
Environmental Molecular Sciences Laboratory
Pacific Northwest National Laboratory
Richland, Washington
Arthur Maki
Mill Creek, Washington
19 June 2006
1
11
BF3: Past High-Resolution Work
Yamamoto, et al.
 J. Chem Phys. 83 1444 (1985); J. Chem Phys. 86 624 (1986). IRmicrowave double resonance spectroscopy of n3 state.
 J. Molec. Spectrosc. 115 333 (1986). IR diode laser spectroscopy of
n2 band.
Olandi, Bauder J. Chem Phys. 86 624 (1986).
 FT-microwave pure rotational spectrum; ground state rotational
constants.
Zeisberger, PhD Thesis, Universität Ulm (1987).
 FTIR spectroscopy of n2, n3, n4, n1 + n4 bands.
Pak, Woods J. Chem Phys. 106 6424 (1997).
 ab initio anharmonic force field [CCSD(T)].
Masiello, Maki, Blake J. Molecular Spectroscopy 234 122 (2005).
 High resolution spectroscopy between 400 and 1650 cm-1.
2
11
BF3: Experiment
Data recorded with Bruker IFS 120HR FTS.
11
BF3 from Voltaix enriched to 99.5 atom% 11B.
Neat samples 0.02 to 2.61 Torr.
20 cm cell (25.00 ± 0.02 °C) for strong bands;
variable pathlength (3.2 to 19.2 m) White cell
(22 °C) for weaker bands.
Instrument resolution 0.0015 to 0.0020 cm-1.
Wavenumber calibration ± 0.0002 cm-1.
3
Energy Term Values
E(v1, v2, v3, v4, l3, l4, k, J) = G(v1, v2, v3, v4, l3, l4) + F (J, k, l3, l4)
Fv (J,k, l) = Bv J(J+1) + (Cv − Bv)K 2 − DJv J 2(J+1)2 − DJKv J(J+1)K 2 − DKv K 4
+ HJvJ 3 (J+1)3+ HJKvJ 2(J+1)2K 2 + HKJvJ(J+1)K 4 + HKvK 6
+ K lv[ −2Cv + JvJ(J+1) + KvK 2 + JJvJ 2(J+1) 2
+ JKvJ(J+1)K 2 + KKvK 4]
± splitting terms
Ground and l = 0 state splitting term
±  3K v [J(J + 1)][J(J+1) − 2] [J(J+1) − 6]
Splitting term for vibrational states with l  0
±  2K  −1l tv[J(J+1)] [J(J+1) − 2] ±  2K  2l tv[J(J+1)] [J(J+1) − 2]
4
Coupling Terms
l-Resonance for v3 ≠ 0 or v4 ≠ 0 :
W2, 0, 2 = v4, J, k, l4 | H |v4 , J, k ± 2, l4 ± 2  =
¼[q4 + qJ4J(J + 1) + qk4k(k ± 1)] [(v4 + 1)2 – (l4 ± 1)2] ½
×[J(J + 1) – k(k ± 1)]½ [J(J + 1) – (k ± 1) (k ± 2)]½
similarly for W2, 2, 0
l-Resonance for v3 ≠ 0 and v4 ≠ 0 :
W0, 2, -2 =  v3, v4, J, k, l3, l4 | H |v3, v4 , J, k , l3 ± 2, l4 ∓ 2  =
[r34 + r34J J(J+1)]
Wk,l3,l4
k – l = 0, or ±3, or ± 6, where l = l3 + l4
5
Coupling Terms
W4, 4, 0 = v3, J, k, l3 | H |v3 , J, k ± 4, l3 ± 4  =
w4, 4, 0 [J(J + 1) – k(k ± 1)]½ [J(J + 1) – (k ± 1) (k ± 2)]½
×[J(J + 1) – (k ± 2) (k ± 3)]½ [J(J + 1) – (k ± 3) (k ± 4)]½
W2, -4, 0 = v3, J, k, l3 | H |v3 , J, k ± 2, l3 ∓ 4  =
½[Q3 + QJ3J(J + 1)] [J(J + 1) – k(k ± 1)]½
× [J(J + 1) – (k ± 1) (k ± 2)]½
W2, 0, -1 =  v1, v2, v3, v4, J, k, l3, l4 | H |
v1 – 1, v2 + 2, v3, v4 – 1 , J, k ± 2, l3, l4 ∓ 1  =
± w2, 0, -1{¼ v1 [v2 + 1] [v2 + 2] [v4 ± l4]
×[J(J + 1) – k(k ± 1)] [J(J + 1) – (k ± 1) (k ± 2)]}½
6
Resonance Terms
Fermi Resonance:
v3, v4, J, k, l | H | v3 – 1, v4 + 3, J, k, l  =
w3444 + w3444JJ(J + 1) +w3444Kk2
v1, v4 Vibrational Resonance:
v1, v4, J, k, l4 | H |v1 – 1, v4 + 2, J, k, l4  =
w144 + w144J J(J+1)
7
11
B
C
DJ
DJK
DK
HJ
HJK
HKJ
HK
0
N
107
107
107
1012
1012
1012
1012
1013
BF3: Ground State
This Work
0.34504016(9)a
0.17217354(5)
4.29971(37)
7.59185(70)
3.55138(60)
1.2982(51)
5.052(14)
6.154(18)
2.366(10)
0.380(51)
23,557
Zeisberger Thesis
0.34504113(50)
0.17217389(162)
4.3009(32)
7.5932(74)
3.5444b
1.323(60)
5.153(198)
6.29(28)
2.469b
0.70(24)
3951
Oldani & Bauder
0.34504060(100)
0.17217368(53)
4.2986(120)
7.5906(87)
3.5488(80)
1.204(380)
5.07(33)
6.34(45)
2.505b
60
a. The uncertainty (two standard deviations) in the last digits is given in parentheses.
b. Fixed by the planarity conditions.
E. Zeisberger, PhD Thesis, Universität Ulm, 1987.
M. Olandi, A. Bauder, J. Chem. Phys. 86 624 – 628 (1987).
8
11
BF3: Vibrational Modes
a2 ″
a1 ′
n2
n1
n3
n4
e′
e′
9
11
BF3: Vibrational Transitions
Below 1650 cm-1
Transition
000011000000
000020000011
000022000011
000031000020
000031000022
000033000022
010011010000
100011100000
001100100000
110000100000
010000000000
010011000011
020000010000
100011000000
001100000000
110000000000
n0 (cm-1)
479.359125(8)
479.959325(22)
480.332562(21)
480.93771(23)
480.56407(23)
481.30092(27)
480.277469(20)
475.480443(42)
568.104927(28)
687.896403(27)
691.214775(11)
692.133119(20)
693.751793(43)
1361.323664(42)
1453.948096(5)
1573.739624(16)
N
5159
1592
1699
95
37
276
801
211
2451
585
4589
2204
2366
3138
5650
1458
Jmax/Kmax
107/104
91/89
96/94
22/21
25/22
50/49
63/58
42/42
53/44
56/55
95/89
70/56
70/56
82/80
70/70
67/60
RMS dev (cm-1)
0.000093
0.000140
0.000246
0.000262
0.000284
0.000214
0.000136
0.000163
0.000200
0.000143
0.000130
0.000137
0.000175
0.000152
0.000218
0.000174
The uncertainty (two standard deviations) in the last digits is given in parentheses.
10
11
BF3: Vibrational Transitions
Below 1650 cm-1
Transition
010020000020
010022000022
030000020000
110011100011
020011010011
100020000011
100022000011
001111000011
110011000011
n0 (cm-1)
693.03993(7)
693.04595(5)
696.16025(6)
688.78687(7)
694.63618(4)
1358.20381(6)
1358.37423(4)
1452.56812(14)
1570.75141(7)
N
227
515
298
88
473
481
861
80
574
Jmax/Kmax RMS dev (cm-1)
43/30
0.000185
48/41
0.000165
57/54
0.000235
31/20
0.000246
48/41
0.000188
56/56
0.000217
64/64
0.000227
46/38
0.0004032
42/42
0.000280
The uncertainty (two standard deviations) in the last digits is given in parentheses.
11
11
BF3: Vibrational Transitions
Above 1650 cm-1
Transition
100022000000
020011000000
001111000000
002200100000
030000000000
011100000000
200011000000
101100000000
101111000000
002200000000
300011000000
201100000000
201111000000
102200000000
003100000000
n0 (cm-1)
1837.73336(4)
1866.12842(4)
1931.92724(14)
2019.53758(10)
2081.12682(6)
2139.68300(14)
2240.94976(3)
2336.26787(22)
2810.71293(8)
2905.38079(10)
3118.20602(6)
3216.32404(7)
3687.1449(9)
3783.84618(8)
4310.26988(28)
N
1118
942
2039
854
417
2606
2918
3048
773
2028
1375
1778
263
1386
447
Jmax/Kmax RMS dev (cm-1)
50/40
0.000439
51/43
0.000282
59/59
0.000336
55/49
0.000359
55/54
0.000331
106/101
0.000296
88/80
0.000255
64/52
0.000354
54/46
0.000367
93/91
0.000330
73/64
0.000370
57/46
0.000355
43/43
0.000708
81/76
0.000395
49/34
0.000759
The uncertainty (two standard deviations) in the last digits is given in parentheses.
12
11
n3, e′
BF3: n1 / n1 + n2 Bands
n1+n2, A2″
Energy
n1+n4, E′
n1, a1′
The 110000 – 000000, 110000 – 100000,
001100 – 100000, and 001100 – 000000,
were used to determine the constants
for 100000 and 110000.
Ground State
13
14
15
11
BF3: Coupling Terms for 200011
and 300011 States
Each of the pairs of states, 200011 and 120000 and 300011 and 220000 is
coupled by a W2, 0, -1 Coriolis interaction described by
v1 ± 1, v4 ± 1,  l4 ± 1, v2 ∓ 1.
Crossing points are between k = 25, l = 1 and k = 26, l = 1 of 200011 and
k = 27, l = 0 and k = 28, l = 0 of 120000. Crossing points are between k =
25, l = 1 and k = 26, l = 1 of 300011 and k = 28 of 220000.
An l-resonance term, W2,0,2, must also be included in the fit.
The 120000 and 220000 states are A′1 symmetry and are not observed
directly from the ground state.
16
11
Constant
G(v,l)
Cb103
B103
DJ109
DJK109
DK109
HJ1012
HJK1012
HKJ1012
HK1012
C
J107
K107
JJ1011
JK1011
KK1011
qv104
qvJ109
qvK109
tv109
w2,0,-1 104
200011
2240.94976(3)
0.937713(55)
0.91826(8)
4.49(6)
6.95(14)
7.44(9)
0.074(13)
0.33(5)
0.25(6)
0.165(21)
0.1243688(8)
20.066(31)
10.583(28)
9.38(57)
15.1(12)
9.10(67)
7.5498(13)
4.903(57)
49.5(37)
0.516(35)
0.3104(39)
BF3
120000
2264.327(10)
[0.2206]c
0.438(7)
[3.5]
[3.2]
[0.27]
[0.0]
[0.0]
[0.0]
[0.0]










300011
3118.20602(6)
1.34469(16)
1.61660(27)
6.17(28)
10.33(54)
9.96(32)
0.100(48)
[0.0]
1.16(18)
0.85(14)
0.1186588(22)
22.101(85)
9.510(82)
1.18(21)
[0.0]
1.61(23)
7.9055(77)
3.26(81)
[0.0]
[0.5]
0.321(9)
220000
3141.688(13)
[0.100]
1.243(24)
[5.09]
[7.00]
[2.5]
[0.0]
[0.0]
[0.0]
[0.0]









17
18
19
11
BF3: The 110011 and 030000 States
The 110011 state is E symmetry and is accessed by the hot bands
110011  000011 and 110011  100011.
The 030000 state is A2 symmetry and is accessed by 030000  000000
and the hot band 030000  020000.
The 110011 and 030000 states are coupled through a Coriolis term
involving w2, 0, -1.
w2, 0, -1 is not well determined because there are no measured
transitions for which the separation of the interacting levels is small.
20
11
BF3: The 010020 and 010022 States
These states have been observed in the hot bands 010020 – 000020
and 010020 – 000022 near 693 cm-1.
Apart from l-resonance between l = 0 and l = ± 2 levels, no
perturbations are expected.
21
11
Constant
G(v,l)
Cb103
B103
DJ109
DJK109
DK109
HJ1012
HJK1012
HKJ1012
HK1012
C
J107
K107
qv104
qvJ109
qvK109
tv109
v1013
w2,0,-1104
110011
2050.11053(7)
0.25508(71)
0.06047(25)
4.29(20)
11.0(13)
0.07(167)
[0.0]c
[0.0]
[0.0]
[0.0]
0.1301856(36)
18.14(13)
14.51(29)
7.1795(45)
4.35(47)
[1.5]
0.80(20)

0.46(7)
BF3
030000
2081.12682(6)
0.79666(13)
0.29216(20)
3.46(13)
0.66(26)
1.94(19)
[0.0]
[0.0]
[0.0]
[0.0]







0.22(31)
010020
1652.35840(7)
0.06480(16)
1.06120(14)
3.74(8)
9.71(20)
6.83(19)
[0.017]
[0.054]
[0.15]
[0.085]



6.7188(14)
4.43(11)
[0.26]

[0.0]

010022
1652.73764(5)
0.06651(15)
1.05758(12)
[3.74]
[9.71]
[6.83]
[0.017]
[0.054]
[0.15]
[0.085]
0.1367812(7)
15.398(16)
14.844(21)



[0.0]

22
23
11
BF3: The 100020,2 and 020011 States
These states are the upper levels of five vibrational transitions:
100020 – 000011, 100020 - 000011 , 100020 – 000000, 020011 – 000000 , 020011
– 001011 and are well determined.
The expected k ± 2, l4 ∓ 1 interaction between 100020 and 020011
states is not observed because the separation of these states is large
and there is insufficient data at the expected crossing points.
24
11
Constant
G(v,l)
Cb103
B103
DJ109
DJK109
DK109
HJ1012
HJK1012
HKJ1012
HK1012
C
J107
K107
JK1011
qv104
qvJ109
qvK109
tv109
v1013
w2,0,-1 104
020011
1866.12842(4)
0.43334(12)
0.67767(13)
3.24(9)
4.52(21)
1.59(17)
[0.0]c
[0.0]
[0.0]
[0.0]
0.1371404(11)
15.158(31)
14.522(38)
[0.0]
6.7706(34)
4.97(30)
[2.9]
0.54(16)

[0.0]
BF3
100020
1837.56294(6)
0.70790(17)
0.24370(16)
4.60(8)
10.08(20)
11.29(18)
[0.02]
[0.10]
0.11(4)
[0.12]




7.1180(22)
3.75(17)
[0.21]

[0.0]

100022
1837.73336(4)
0.70360(13)
0.23605(12)
[4.60]
[10.08]
[11.29]
[0.02]
[0.10]
[0.11]
[0.12]
0.1302787(8)
17.518(19)
12.439(28)
2.81(11)



0.47(44)

25
26
27
Energy
11
BF3: The 101100 and 100031,3 States
Fermi Resonance
020022, A′1 + E ′
101100, E ′
Coriolis Coupling
100031,3, A′1 + A′2 + E ′
Ground State
28
Constant
101100
G(v,1)
2336.2008(29)
G(v,3)G(v,1)
C103
1.02964(34)
3
B10
2.12053(32)
9
0.980(79)
DJ10
DJK109
1.93(17)
9
1.83(20)
DK10
12
0.095(16)
HJ10
12
HJK10
[0.4]
12
[0.6]
HKJ10
12
HK10
[0.2]
0.122306(30)
Cv
7
7.979(60)
J10
7
K10
1.87(11)
4
0.5294(30)
qv10
9
qvJ10
6.80(10)
9
341.(13)
qvK10
9
3.449(15)
tv10
w3444
1.288(28)
5
w3444J10
2.81(53)
5
3.94(77)
w3444K10
5
[0.0]
q344410
[0.0]
q3444J108
100031,3
2311.519(15)
[0.73]
[0.64]
[0.74]
[0.68]
[26.51]
[0.15]
[0.0]
[0.0]
[0.0]
[0.0]
[0.1305]
[15.4]
[14.8]
[6.7]
[0.0]
[0.0]
[0.7]
201100
3216.1932(58)
1.3054(12)
2.80117(33)
1.37(7)
5.37(28)
2.18(16)
[0.0]
[0.0]
[0.0]
[0.0]
0.116564(37)
11.28(15)
0.44(10)
0.7666(55)
6.02(26)
243.(28)
3.498(43)
2.19(5)
[3.9]
[8.5]
[0.0]
[0.0]
200031,3
[3179.625]
[0.73]
[0.966]
[0.0589]
[0.68]
[26.51]
[0.15]
[0.0]
[0.0]
[0.0]
[0.0]
[0.1245]
[15.4]
[14.8]
[6.9]
[0.0]
[0.0]
[0.7]
29
30
11
BF3: Forbidden Band
011100 – 000000 E″ − A′1 transition has been observed near 2140
cm-1.
The rotational transitions of the band obey electric dipole allowed
selection rules k = ± 2, l = ∓ 1.
Line positions fit by taking into account l-resonance and a
vibrational resonance with the nearby 010031 state. This state was not
observed directly.
Intensity of the band activated by rotation-dependent terms in the
Hamiltonian: Coriolis coupling with 2n3, centrifugal mixing with n2.
Details given in A. Maki, J.K.G. Watson, T. Masiello, T.A. Blake,
J. Molec. Spectrosc. 238 (2006).
31
11
Constant
G(v,l)
(l4 = 3)(l4 = 3)
Cb  103
 B  103
 DJ 109
 DJK  109
 DK  109
 HJ  1012
 HJK  1012
 HKJ  1012
 HK  1012
(C)v
J  107
K  107
JJ  1011
JK  1011
KK  1011
qv  104
qvJ  109
qvK  109
tv  109
w3444
w3444J  105
w3444K  105
q3444  105
q3444J  108
BF3
011100
2139.65177(30)
0.463498(79)
1.32616(15)
0.014(31)
1.114(73)
2.520(63)
[0.0313]
[0.096]
[0.0]
[0.036]
0.127633(16)
7.857(72)
1.351(92)
0.34(15)
3.53(30)
0.73(25)
1.729(83)
25.6(53)
32.(42)
3.50(14)
0.4150(18)
0.35(13)
5.9(18)
0.54(11)
[0.0]
010031
2134.170(2)
[0.031]c
1.5779(77)
[5.1]
[15.4]
[10.5]
[0.0]
[0.0]
[0.0]
[0.0]
[0.136788]
[15.4]
[14.8]
[0.0]
[0.0]
[0.0]
6.414(15)
[5.0]
[0.0]
[0.72]
010033
2134.1700.648(15)
0.747(27)
[0.031]
[1.5779]
[5.1]
[15.4]
[10.5]
[0.0]
[0.0]
[0.0]
[0.0]
[0.136788]
[15.4]
[14.8]
32
33
11
BF3: The 0020,200 and 001131 States
The 0020,200 levels do not fit within the measurement precision
(0.0004 cm-1) because of the interaction of many nearby
(unmeasured) states: 002000 (l = 0) A′1 (2871 cm-1)
001131 (l = 2) E′ (2885.7 cm-1)
001133 (l = 4) E′ (2887.6 cm-1)
00113-3 (l = 2) E′ (2884.0 cm-1)
00113-1 (l = 0) A′1 (2884.5 cm-1)
000060 (l = 0) A′1 (2887.1 cm-1)
000062 (l = 2) E′ (2887.4 cm-1)
000064 (l = 0) A′1, A′1
000066 E′,
210011 (l = 1) E″ (2930 cm-1).
Fit was made assuming a single “effective” perturbing level. W4,4,0, W2,-4,0
terms are required for the fit.
34
11
Constant
G(v,l=2)
G(v,l=2)G(v,l=0)
C103
B103
DJ109
DJK109
DK109
HJ1012
HJK1012
HKJ1012
HK1012
C 3
3J107
3K107
3JJ1011
3JK1011
3KK1011
3KKK1015
C 4
4J107
4K107
q3104
q3J109
q3K109
tv109
Qv 105
QvJ 108
w4,4,0 108
w3444
w3444J104
w3444K104
0020,200
2905.36575(13)
[24.64]
1.50946(19)
2.88856(11)
0.110(82)
5.98(18)
1.90(13)
0.280(16)
0.925(42)
1.246(31)
[0.0]
0.1271680(10)
6.048(22)
1.093(24)
0.186(42)
3.29(7)
1.01(7)
1.53(6)



[1.88]
[7.57]
[68.6]
1.55(20)
1.862(56)
0.521(42)
0.392(21)
0.5470(25)
0.363(11)
[0.23]
BF3
001131
2885.480(35)
[1.05]
[0.0]
35.4(11)
[0.0]
[0.0]
[0.0]
[0.0]
[0.0]
[0.0]
0.1235(5)
[6.2]
[0.507]
[0.0]
[0.0]
[0.0]
[0.0]
[0.1364]
[15.5]
[14.9]
[0.0]
[0.0]
[0.0]
[0.0]
Also used in the fit:
G(v,l3 = 1, l 4 = 1)  G(v,l3 = 1,l4 = 1) = 2.18;
G(v,l3 = 1, l 4 = 1)  G(v,l3 = 1,l4 = 3) = 3.63; and
G(v,l3 = 1, l 4 = 1)  G(v,l3 = 1,l4 = 3) = 2.93.
35
Vibrational and Rotational Constants
G(n,l) =  wi (vi + di/2) + 
 xij (vi + di/2) (vj + dj/2)
+
 xij lilj +    yijk(vi + di/2) (vj + dj/2) (vk + dk/2)
+
  yijk(vi + di/2) ljlk
Bv = Be −  aiB(vi + di/2) + 
+
 gijB (vi + di/2) (vj + dj/2)
 gijB lilj + …
36
BF3: Vibrational Constants
Constant
w1
w2
w3
w4
x11
x22
x33
x33+x33
x44
x12
x13
x14
x23
x24
x34
x33
x44
x34
r34
10
BF3
Calc.a
897.2425
889.304
722.7600
1530.4130
484.0471
1.157816 1.122
1.334472
7.6531
1.276102
0.394659
3.373784 3.658
4.479131 4.689
3.115432 3.092
[5.4]fixed
0.943248
3.111345
6.3769
0.095120
0.712629
6.131
11
BF3
Calc.a
897.3266
889.304
694.9463
1477.7216
482.1097
1.169222 1.122
1.268507
7.68
1.28184
0.393414
3.318375 3.608
3.607115 3.778
3.878666 3.829
5.527717
0.918342
2.543905
[6.4]fixed
0.093304
1.0939
5.978
Calc.b
899.3
700.1
1493.1
483.7
1.12
1.16
7.34
1.18
0.32
3.53
6.48*c
1.23*
5.4
0.94
4.05*
6.16
0.11
0.57*
5.78
a. R. Kirkpatrick, T. Masiello, A. Weber, J.W. Nibler, J. Molec. Spectrosc. 237 97 (2006).
b. Y. Pak, R.C. Woods, J. Chem. Phys. 106 6424 (1997).
c. The asterisks indicate deperturbed anharmonicity constants.
37
BF3: Rotational Constants
B-axis
Constant
Be or Ce
a1  103
a2  103
a3  103
a4  103
g11  105
g22  105
g33  105
g44  105
g44  105
g12  105
g13  105
g14  105
g23  105
g24  105
g34  105
a
10
BF3
0.3462819
0.68469
0.11866
1.51141
0.50920
0.0070
1.103
0.339
0.186
0.094
6.698
1.754
0.978
[0.566]a
1.108
1.202
C-axis
11
BF3
0.3462679
0.68198
0.12814
1.43955
0.48453
0.0730
1.079
0.530
0.199
0.090
5.486
0.300
2.246
0.566
0.985
2.080
10
BF3
0.17314425
0.34288
0.28046
0.88884
0.10798
0.0145
0.432
0.046
0.120
0.048
0.979
2.792
2.828
[1.135]
0.280
3.125
11
BF3
0.17311506
0.32270
0.27087
0.84807
0.13384
0.4315
0.463
0.536
0.114
0.048
0.916
5.729
8.536
1.135
0.302
8.046
The values enclosed in square brackets were fixed at the value for the other isotopomer.
38
The End
39
11
File
A
B
B1
C
D
E
F
BF3: Experiment
Region
(cm-1)
1750 - 2350
2200 - 2600
2200 - 2600
2700 - 3100
3000 - 3400
3500 - 3950
4100 - 4600
Pathlength Pressure Resolution Calibration
(m)
(Torr)
(cm-1)
Gas/Vapor
12.8
3.86
0.0025
CO
19.2
0.15
0.0025
CO2
19.2
1.69
0.0025
CO2
12.8
0.82
0.0025
OCS
25.6
4.90
0.0035
OCS
32.0
3.55
0.0030
CO2
38.4
4.12
0.0035
CO
40
11
File
J
T
L
Q
S
G
N
O
BF3: Experiment (cont’d.)
Region
(cm-1)
400 – 600
400 – 640
600 – 800
600 – 900
600 – 900
1200 – 1600
1200 – 1600
1500 – 1700
Pathlength
(m)
0.20
12.8
0.20
6.4
3.2
0.20
3.2
19.2
Pressure
(Torr)
2.46
1.10
0.80
0.56
0.02
0.18
0.25
2.61
Resolution Calibration
(cm-1)
Gas/Vapor
0.0015
H 2O
0.0015
H 2O
0.0016
CO2
0.0015
OCS
0.0015
OCS
0.0020
N 2O
0.0020
N 2O
0.0020
OCS
41
CARS Spectra of 10BF3 and 11BF3
J=K=24
CARS Spectrum - n 1 mode of 10BF 3
J=K=12
*
J=K=0
Calc.
Exp.
884.2
884.4
884.6
884.8
885
885.2
885.4
885.6
885.8
886
-1
Raman Shift (cm )
R. Kirkpatrick, T. Masiello, A. Weber, J.W. Nibler, J. Molec. Spectrosc. 237 97 (2006).
42
Symbols and Signs
Wk,l3,l4
k – l = 0, or ±3, or ± 6, where l = l3 + l4
A Hamiltonian matrix is set up for each transition fit including term
values, splittings, and coupling terms. The energy level crossing
level of interacting states is noted.
If there is a separation of A1 and A2 states, then if the constant
causing the splitting is positive, A2 is above A1 if J is even and below
if J is odd.
43
11
BF3: Statistical Weights
Symmetry of Vib. State
A 1' & A 1"
A 2' & A 2"
l = +1
Rotational Symmetry
K= 0, J even
K= 0, J odd
K= 3n + 1, n=0,1,2,etc.1
K= 3n + 2, n=0,1,2,etc.
K= 3n + 3, n=0,1,2,etc.
0
2
1
1
2
2
0
1
1
2
0
0
2
1
1
E' and E"
l = 1 l = +2
1
1
1
2
1
1
1
1
2
1
l = 2
0
0
2
1
1
44
45
11
Constant
G(v,l)
C103
B103
DJ109
DJK109
DK109
HJ1012
HJK1012
HKJ1012
HK1012
C v
J107
K107
JJ1011
JK1011
KK1011
qv104
tv109
Qv 105
w3444
w3444J104
w144
w144J104
102200
3783.85089(11)
1.69825(39)
3.59165(23)
0.51(13)
11.89(41)
5.45(52)
[0.0]
0.59(9)
[0.0]
0.05(10)
0.1214750(15)
9.545(64)
1.293(69)
0.53(28)
9.38(66)
2.46(74)
[0.5320]
0.26(18)
1.954(27)
102000
[3756.085]
[1.69825]
[3.59165]
[0.51]
[11.89]
[5.45]
[0.0]
[0.59]
[0.0]
[0.05]






[0.0]

BF3
101-133
3763.062(28)
[1.40]
0.680(20)
[1.77]
[20.6]
[4.92]
[0.28]
[0.72]
[0.47]
[0.44]
0.1733(4)
[15.0]
[14.0]



[0.0]

101131
3764.79(21)
[1.40]
[0.680]
[1.77]
[20.6]
[4.92]
[0.28]
[0.72]
[0.47]
[0.44]
0.0236(16)
[15.0]
[14.0]



[0.0]
0.3780(8)
0.642(13)
0.1110(56)
002022
3830.219(48)
[1.70]
1.7869(23)
[1.30]
[13.0]
[5.20]
[0.28]
[0.72]
[0.47]
[0.44]
0.12848(26)
[15.0]
[14.0]
[0.0]
0.7533(10)
0.0340(38)
46
47
Constant
G(v,l=0)G(v,l=4)
G(v,l=2)
G(v,l=2)G(v,l=0)
C103
B103
DJ 109
DJK109
DK109
HJ1012
HJK1012
HKJ1012
HK1012
C 3
3J107
3k107
3JJ1011
3JK1011
3KK1011
C 4
4J107
4K107
4KK1011
q3104
q3J109
q3K109
q4104
q4J109
q4K109
r34
r34J103
p34104
t34109
w2,-2,-2102
w3444
w3444J105
w3444K105
(001111)0,2

1931.87383(14)b
2.1878(41)
0.76941(29)
0.93588(30)
2.54(25)
8.96(77)
5.65(60)
0.35(9)
6.3(4)
10.4(5)
4.39(23)
0.12383(11)
[6.2]
[0.507]
[0.3]
[3.3]
[0.73]
0.13820(11)
12.68(9)
16.73(9)
[0.0]
[1.88]
[7.6]
[68.0]
6.160(8)
7.3(5)
10.6(32)
5.9776(84)
0.0319(12)
0.1501(15)
41.9(4)
[0.0]
0.7281(11)
0.5(2)
[0.0]
(000040,2,4)
[1.49]a
1922.001(11)
[0.37]
[0.409]
2.117(23)
333.5(72)
[135.]
[100.]
[0.0075]
[0.144]
[0.30]
[0.156]






0.13828(15)
[16.9]
[16.4]




[7.0]
[0.0]
[0.0]


[0.0]
[0.7]
(101111)0,2
2810.60722(8)
3.054(14)
1.1161(8)
1.62721(42)
5.72(50)
29.0(15)
13.3(16)
[0.0]
8.1(11)
15.4(21)
[0.0]
[0.1180]
[6.2]
[0.5]
[0.0]
[0.0]
[0.0]
0.133179(4)
9.12(20)
16.5(5)
88.(8)
[0.54]
[0.0]
[0.0]
6.918(13)
[0.0]
145.(20)
4.867(16)
[0.0]
0.1427(32)
3.6(18)
[0.0]
[1.6]
[2.8]
[4.0]
(100040,2,4)
[1.12]
[2786.495]
[0.28]
[0.74]
[1.41]
[116.]
[291.]
[232.]
[0.0]
[0.0]
[0.0]
[0.0]






[0.1378]
[16.9]
[16.4]




[7.0]
[0.0]
[0.0]


[0.0]
[0.7]
(201111)0,2
3687.1449(9)
3.864(26)
1.370(22)
2.3185(51)
34.6(28)
148.(11)
14.(11)
[0.0]
[0.0]
[0.0]
[0.0]
[0.1120]
[6.2]
[0.0]
[0.0]
[0.0]
[0.0]
0.12858(13)
20.9(42)
21.4(72)
[0.0]
[0.73]
[0.0]
[0.0]
7.813(57)
[0.0]
[0.0]
5.069(27)
0.250(10)
[0.1428]
[0.9]
0.151(10)
[0.0]
[0.0]
[0.0]
48
49
11
Constant
G(v, l)
C  103
B  103
DJ  109
DJK  109
DK  109
C
J  107
K  107
qv  104
BF3
003100
4310.26988(28)
1.8260(39)
4.1590(7)
1.07(45)
10.3(25)
30.1(48)
0.130228(23)
6.48(86)
3.8(25)
1.927(11)
50