KARIMGANJ COLLEGE, KARIMGANJ
An algebraic approach to the study of the
vibrational
spectra of HCN
Presented by
Bishal Baidya
Roll : 062219 Submitted for the partial fulfillment
No : 200200230 of
B.Sc. 6th Semester
in
Physics Honours
Department of Physics date 1
Content
✔ Introduction
✔ Theory and fundamentals
✔ Results
✔ Conclusion
✔ References
An algebraic approach to the study of the vibrational spectra of HCN Month - Year2 2
1. Introduction
With the development of more powerful experimental techniques, molecular
spectroscopy is now going through an exciting time of renewed interest.
Tunable, stable and powerful lasers are now available to create highly excited
levels [1,2] with unprecedented resolution. It should be noted that molecular
spectroscopy is undergoing a radical change not simply due to the
development of more powerful experimental techniques.
Various approaches have been used so far in the study of molecular spectra. Out
of these, two important approaches are –
(i) Dunham expansion and
(ii) Potential approach.
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In the Lie algebraic method, there is provision to Study a molecule both using a
normal and a local Hamiltonian. There are several molecules that can be very well
approximated by a local Hamiltonian, HCN being an important molecule in this
category. Van Roosmalen et al. studied the HCN molecule using the local
Hamiltonian [3], as did Iachello and Levine in their work. Oss also studied the HCN
molecule using the local Hamiltonian. Using the Lie algebraic method, in this study
the vibrational energy levels of HCN (in cm1) were calculated using the local
Hamiltonian.
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2. Theory and fundamentals
Local-mode Hamiltonian for HCN (a linear triatomic molecule)
Using the concepts of the algebraic models for linear triatomic molecules we can
construct the local mode Hamiltonian as –
Hlocal = E0 + A1C(O(41)) + A2C(O(42)) + A12C(O(412)) + BC(O(312)).
Where, E0 is the zero of the energy scale, A1, A2, A12 , A12 are the algebraic
parameters & C(O(41)), C(O(42)), C(O(412)), C(O(412)), BC(O(312)) are the bilinear
Casimir invarients.
An algebraic approach to the study of the vibrational spectra of HCN
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Calculation of Eigenvalues
E(N1, N2ω1, ω2, τ1, τ2, J , MJ)= E0 + A1 ω1(ω1 + 2) + A2 ω2(ω2 + 2) + A12[τ1(τ1 + 2)
+ τ22] + BJ(J + 1). (1)
We can now convert above equation into the usual form by introducing the local
vibrational quantum numbers
ω1 = N1 - 2νa, ω2 = N2 - 2νc, τ1 = N1 + N2 - 2νa – νb - 2νc, τ2 = 1b. (2)
Equation (1) can be converted, using equation (2), into
E(νa,νb1b,νc) = E0/ - 4A1[(N1 + 1)νa - νa2] – 4A2[(N2 + 1)νc – νc2] – A12[2(N1 + N2 + 1)
(2νa + νb + νc) – (2νa + νb + 2νc)2 + 1b2].
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3. Results
A comparison of the vibrational energy levels of HCN and those calculated in the strict
local limit is shown in table. Using the established norms the vibron numbers N 1 and N2
and other algebraic parameters A1, A2 and A12 were determined.
Table:- Vibrational energy levels of hydrogen cyanide (in cm -1).
ν1 ν 2
12
ν3 Exp. Ⅰb
Calc. Δa e
0 20 0 1411.43 1412.972 -1.542
1 20 0 3501.13 3501.872 -0.742
3 00 3 15 710.53 15 713.016 -2.486
0 11 0 711.98 710.264 +1.716
0 31 0 2113.46 2115.68 -2.22
1 11 0 2805.58 2806.72 -1.14
0 11 1 4004.17 4002.072 +2.098
2 11 0 4878.27 4878.192 +0.078
1 11 1 6083.35 6083.416 -0.066
0 42 0 2818.16 2818.388 -0.288
b
This study: N1 = 140, N2 = 47, A1 = - 1.234, A2 = - 10.034, A12 = - 1.889. Δ(r.m.s.) = + 0.5308
e
Δ a = (Exp.–Calc.).
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4. Conclusion
Using less parameter here by using the lie algebraic method we are able to obtain
better results for determining the vibrational spectra of Hydrogen cyanide (A linear
triatomic molecule).
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5. References
[1] F.J. Duarte (Ed.), Tunable Laser Applications, second edition, CRC, New
York, 2009.
[2] Y.Y. Jiang, A.D. Ludlow, N.D. Lemke, R.W. Fox, J.A. Sherman, L.S. Ma,
C.W. Oates, Nat. Photon. 5 (2011)
[3] O. van Roosmalen, F. Iachello, R. D. Levine, and A. E. L. Dieperink, J.
Chem. Phys. 79, 2515 (1983).
[4] N.K. Sarkar, J. Choudhury, S.R. Karumuri, R. Bhattacharjee, Vib.
Spectrosc. 56 (2011) 99.
[5] N.K. Sarkar, J. Choudhury, R. Bhattacharjee, Indian J. Phys. 82 (2008)
767.
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