ACCURATE ANALYTIC POTENTIAL FUNCTIONS FOR THE A 3 Π 1 and X 1 Σ + STATES OF IBr T.Yukiya * , N. Nishimiya * , M.Suzuki * , and R. J. LeRoy ** *Dept. of Electronics and Information Technology, Tokyo Polytechnic University, Iiyama 1583, Atsugi City, Kanagawa 243-0297, Japan ** Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada Jun. 16, 2014 T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun. 16, 2014 1 / 22
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ACCURATE ANALYTIC POTENTIAL FUNCTIONS FOR THE A31 and …
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N5 p6q3 N5 p5q3 N5 p5q4 N6 p5q3 N6 p5q4
(n o rm
dd =
yobs(i) :measured value ycalc(i):calculated value unc(i) :The
estimated
uncertainty of datum N :The total number of data w(i) :the normal
data weights wrob(i):the robust weights
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 15 / 22
Long-Range Extrapolation behavior of the Potential
The long-range extrapolation behaviour of a number of fitted MLR
models for the A 3Π1 state of IBr T.Yukiya (Tokyo Polytechnic
University) The A-X System of IBr Jun. 16, 2014 16 / 22
Number of Λ-Type Doubling Constants
Number of Lambda-Type Doubling terms V(r) function
Robust weights
V
/r **
Data
Region
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
V
/r **
Data
Region
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 17 / 22
Number of Centrifugal Born–Oppenheimer Breakdown Terms
Number of Centrifugal BOB terms Centrifugal BOB function
Robust weights
UNC of v(A)=26- 29 are 2.0cm−1.
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 18 / 22
......
Values Error Values Error Values Error Te 12369.6142 0.0097 De
2428.2870 0.0084 Re 2.8653212 2.2×10−5
C5 4.3635×104 – C6 1.132 ×106 – C8 2.42×107 – De(X) 14797.90124
0.00086 uBr
0 (X) 0.241 0.0041 β0 1.1080742 0.00016 β1 0.403637 0.00013 β2
-1.33961 0.00023 β3 -0.70070 0.00090 β4 1.6983 0.0041 β5 1.2010
0.017 β6 -1.9160 0.039 β7 -4.1465 0.13 β8 1.50 0.10 β9 9.7 0.34 β10
-1.3230 0.088 β11 -8.687 0.29 tBr 0 0.0 – tBr
1 -0.0048 0.00034 tBr 2 0.0209 0.00069
ω0 0.00288 8.6×10−5 ω1 -0.069 0.011 ω2 0.17 0.038 ω3 0.513
0.037
’Robust’ is used in this calculation. The constants β0 ∼ β6 of the
X were constrained into below values.
......
Values Error Values Error Values Error C5 -1.21×103 – C6 1.156 ×106
– C8 2.42×107 – De 14797.9* Re 2.46898596 6.1×10−8
β0 0.32025489 1.0×10−6 β1 -1.132183 5.5×10−5 β2 -0.652405
5.2×10−4
β3 0.262 7.3×10−3 β4 1.519 0.045 β5 3.41 0.28 β6 5.6 0.79
uBr 0 0.202 0.17
De was constrained into the value reported by E. Wrede. All level
of the A state were independent term values in this
calculation.
. Overall ..
......
For the A State No. of Data: 20741 No. of Param.: 30
dd: 0.93 vmin( A): 3 vmax( A): 29
D-vmax(A): 181 cm−1
For the X State No. of Data: 12103 No. of Param.: 6
dd: 0.735 vmin(X): 0 vmax (X): 19 D-vmax(X): 9880.7cm−1
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 19 / 22
Bυ′ and the first differences for the A state
0.020
0.025
0.030
0.035
0.040
0.045
B v 'c m -1
v'
B v 'x 1 0 4 c m -1
v'
Black lines indicate the parameter generated by DPotFit.
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 20 / 22
Which Bands have trouble?
c a
lc -o
I 79
Br26 f
I 81
Br26 f
I 81
Br26 e
I 79
Br27 f
I 81
Br27 f
I 79
Br27 e
I 81
Br27 e
I 79
Br28 f
I 81
Br28 f
I 79
Br28 e
I 81
Br28 e
I 79
Br29 f
I 81
Br29 f
I 79
Br29 e
I 81
Br29 e
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 21 / 22
Conclusion
Potential function parameter are determined for the A and X
state.
First differential of the Bv of the A state which is calculated by
potfit are compared with parameter calculated by parameter
fitting.
Found that there are something trouble in v(A)=27–29 of
I79Br.
We need to measure the high vibrational level of the A state to
improve accuracy of the potential.
-14.0
-12.0
-10.0
-8.0
-6.0
-4.0
-2.0
0.0
x 1 0 0 0 c m -1
D e = 1 4 7 9 7 .9 c m -1
v"=19
v"=0
v'=3
v'=29
v'=25
Re=2.46898595(6)
Re=2.86530(2) D e = 2 4 2 8 .2 9 4 (8 )c m -1
T.Yukiya (Tokyo Polytechnic University) The A-X System of IBr Jun.
16, 2014 22 / 22
Introduction
Purpose
Potential Function for the A and X states
Direct Potential Fitting