CHIN. PHYS. LETT. Vol. 26, No.

2 (2009) 020308

Vibrational Spectroscopy of CH/CD Stretches in Propadiene: An Algebraic Approach

Joydeep Choudhury1** , Nirmal Kumar Sarkar2 , Srinivasa Rao Karumuri1 , Ramendu Bhattacharjee1
2

Department of Physics, Assam University, Silchar-788011, India Department of Physics, Karimganj College, Karimganj-788710, India

(Received 18 September 2008)

Using Hamiltonian based on Lie algebraic method, the stretching vibrational modes of C3 H4 and C3 D4 molecules are calculated up to higher overtones. The model appears to describe CH and CD stretching modes with less number of parameters. The locality parameter confirms the highly local behaviour of the stretching modes of these molecules.

PACS: 03. 65. Fd, 31. 15. Hz Molecular spectroscopy is an area of active interest and has played an important role to understand and analyse a physical system in both experimental and theoretical approaches. One of the most interesting areas of current research in molecular physics is the study of vibrational ground and excited states of polyatomic molecules. After the recent rapid developments of sophisticated instruments, the molecular spectroscopy is currently going through an exciting time of renewed interest. Two traditional approaches have been used so far in the analysis of experimental data: (i) the Dunham-like[1] expansion of energy levels in terms of rotationvibration quantum numbers and (ii) the solution of Schrdinger equation with o potentials obtained either by modifying ab initio calculations or by more phenomenological methods. The Dunham-like expansions contain a large number of parameters which can not be determined from the few available data and the model based on the solution of many body Schrdinger equation with interatomic o potential becomes cumbersome and dicult to apply in the case of polyatomic molecules. To overcome the diculties arises in analysing the vibrational spectra, third approach the vibron model (the algebraic models) based on Lie algebra[2] was built in the second half of the 20th century. This new model seems to describe the molecular spectra successfully even in complex situations. The algebraic models have been used extensively in a variety of elds: (i) research of spectra of atomic nuclei (interacting boson model)[3] and (ii) spectra of diatomic and triatomic molecules,[4,5] (iii) research of spectra of linear and quasilinear tetratomic molecules,[6] (iv) spectra of tetrahedral molecules,[7] benzene[8] and octahedral molecules,[9] (v) vibrational modes of CH bonds in n-paran molecules,[10] (vi) CH stretching modes of n-alkane[11] and polyethylene.[12] Iachello and Oss presented a brief review of development of algebraic techniques and its application to molecular spectroscopy[13] in last ve years up to 2000. The main features and applications of these methods have been described in a number of books[14,15] and review articles[16] in last few years. Recently we
** To

reported the studies on vibrational spectra of HCN, OCS,[1719] HCCF, HCCD,[20] CCl4 , SnBr4 ,[21] Ni (OEP), Ni (TPP) and Ni porphyrin[22] by an algebraic approach. Propadiene is one of the most extensively studied molecules belonging to the point group D2 . The CH (or CD) stretching vibrational modes of such molecules have been analysed by dierent authors, e.g. Mills and Mompean[23] and Halonen.[24] In this Letter, we initiate the use of algebraic methods to generate stretching modes of CH (CD) bonds in propadiene molecule. The model we use is nothing but a one-dimensional version of the general algebraic model of rotation-vibration spectra of polyatomic molecules. In this model, each bond, , is replaced by an algebra , and the Hamiltonian describing the molecule is written in terms of algebraic bond coordinates. The eigen states, eigenvalues and matrix elements of operators are then found out by algebraic manipulations which are easy to perform. We start with full algebraic Hamiltonian operator for C3 X4 (X=H, D) molecules. The general form of such operator can be written as = + + . (1)

In this expression, describes the stretching modes and is based on (2) algebra; describes the degenerate bending modes and is constructed from the two-dimensional model (3) algebra; provides stretch/bend interactions of several kinds based on the (2)/ (3) scheme.[25] In this study, we neglect and in Eq. (1) due to lack of experimental data for bending mode. We consider the stretching Hamiltonian . For four one-dimensional oscillators CX (X=H, D), we start with the spectrum generating algebras (SGA), 1 (2) 2 (2) 3 (2) 4 (2). Here, the two CC oscillators (bond 5 and 6) are not considered on the basis which may denitely give the stretching vibrations as we mostly focused on CX stretching vibrations. We then construct the local basis given by

whom correspondence should be addressed. Email: choudhuryjoy@rediffmail.com c 2009 Chinese Physical Society and IOP Publishing Ltd

020308-1

CHIN. PHYS. LETT. Vol. 26, No. 2 (2009) 020308

1 (2)

2 (2)

3 (2)

4 (2)

1 (2) 1

2 (2) 2

3 (2) 3

4 (2) . 4

(2)

Table 1. CH (CD) stretching vibrational modes of C3 H4 and C3 D4 molecules. Here the observed values are taken from Ref. [23]. 1 Vibrational level 5 1
1 8

Symmetry 2 1 1 2 1 2 1 1 2 1

C3 H4 calc (cm1 ) obs (cm1 ) 3000.84 3015.6 3000.84 3006.6 3081.25 5946.81 5997.96 6078.37 5946.81 5997.96 6158.78 6025.34 6025.34 8596.68 8863.52 42.89 cm1 5980 6135.5 3085.6 5947.5

C3 D4 calc (cm1 ) obs (cm1 ) 2205.96 2228.9 2205.96 2216.6 2310.51 4448.55 4409.16 4513.71 4448.55 4409.16 4618.26 4551.39 4551.39 6414.12 6547.2 29.53 cm1 4611.4 2321.2 4417.4

25 1 + 5 2
1 5 + 8 21 1 1 + 8 2 28 0 28 2 28

3 (rms)

35 1 + 25

In this expression, we introduce the vibron numbers (X=H,D) which are directly related to the anharmonicity of local CH (CD). The four stretching quantum number 1 , 2 , 3 , 4 are associated with CH (CD) bonds (Fig. 1). The stretching Hamiltonian for uncoupled bonds can be written as () = (1 + 2 + 3 + 4 ). (3)

The operators are the Casimir invariant operators of (2) algebras, = 1, 2, 3, 4. Their diagonal matrix elements in the local basis 1 , 2 , 3 , 4 are of the form = 4 ( ), = 1, 2, 3, 4 (4)

The modes of four equivalent CX bond are now mixed, shifted and split under the action of the operator (adjacent and opposite). The Majorana operator is used to describe local mode interactions in pairs and has both diagonal and non-diagonal matrix elements given by[9] , ; , , ; , = + 2 , , + 1; , 1 , ; , [ ] 1 = ( + 1)( )( + 1) 2 , , 1; , + 1 , ; , [ ] 1 = ( + 1)( )( + 1) 2 , (8) so the general algebraic Hamiltonian operator for describing the CX (X=H,D) stretching modes of propadiene is expressed by =
4 =1

with 1 = 2 = 3 = 4 = . Interbond couplings can be introduced in terms of operators associated with products of (2) and (2) algebras associated dierent, interacting bonds. We are thus led to coupled, stretching Hamiltonian operator ( (1) = 12 + 13 + 14 ) + 23 + 24 + 34 .

4 <=1

4 <=1

(9)

(5)

The term leads to cross-anharmonicities between pairs of distinct local oscillators which is diagonal with matrix elements given by , ; , | | , ; , = 4[( + )2 ( + )( + )]. (6)

The strength of uncoupled and coupled bonds are regulated by parameters ( ), / ( ) and = adj , respectively. The inclusion of in the Hamiltonian conserves the total vibrational (polyad) quantum number.
X 1 C X
2 5 6 4 X

C
3

Thus, the total Hamiltonian for coupled and uncoupled stretching bonds is expressed by (0) (1) = + . (7)

Fig. 1. Bond numbering adopted in the C3 X4 (X=H, D) molecule for its algebraic representation.

In Table 1, we list the results of ts to CH and CD stretching fundamental and overtone modes of

020308-2

CHIN. PHYS. LETT. Vol. 26, No. 2 (2009) 020308

propadiene molecule using the model Hamiltonian (9). From the view of group theory, the four oscillators (C X) describe the fundamental stretching modes ( = 1) 1 given by 1 (1 ), 2 (5 ), and (8 ) irreps. Here 1 represents the symmetry irreps while 1 and 2 represent antisymmetric irreps with respect to 2 perpendicular to the principal axis, and represents twodimensional symmetric irreps with respect to centre of inversion. There are ten stretching vibrational states 0 ( = 2) separates into 1 (25 ), 1 (21 ), 1 (28 ); 2 2 1 1 (28 ); 2 (1 + 5 ) , 2 (28 ); (5 + 8 ) and 1 (1 + 8 ). Out of these states, 31 bands are Raman active and the remaining states are infrared active. As there are very few available data, Table 1 should be considered more a prediction of unknown states rather than a t. It is seen from Table 2 that the parameters are dierent for two molecules. Here (rms) is reported as 42.89 cm1 and 29.53 cm1 for C3 H4 , C3 D4 molecules, respectively. We believe that more satisfactory results will be predicted if the interbond coupling between CH (CD) stretches at opposite ends of the molecules are taken into consideration in spite of their small values. Also, it is to be mentioned here that the large number of observed data may reduce the value of (rms). The vibron numbers for CH and CD bonds, ( ) were xed to = 43 and = 61, calculated from expression {( / ) 2} with experimental potential parameters ( = 2861.6 cm1 , = 64.3 cm1 for C3 H4 and = 2333.7 cm1 , = 30.6 cm1 for C3 D4 ) taken from Refs. [5,24].
Table 2. Fitting parameters of C3 H4 and C3 D4 . C3 H4 C3 D4 ( ) ( ) / ( ) = adj 43 15.98 0.465 0.935 61 7.8 0.345 0.857

CD bond, thus conrming highly local behaviour of the stretching modes of propadiene. Thus, we can say that the algebraic model Hamiltonian is successful in predicting the energies in the complex molecular system. We would like to thank Professor S. Oss for providing initial inspiration for this study. RB and SRK are grateful to DST for providing a research grant.

References
[1] Dunham J L 1932 Phys. Rev. 41 721 [2] Iachello F 1981 Chem. Phys. Lett. 78 581 [3] Iachello F and Arima A, 1974 Phys. Lett. B 53 309 Arima A and Iachello F 1975 Phys. Rev. Lett. 35 1069 [4] Iachello F and Levine R D 1982 J. Chem. Phys. 77 3046 [5] van Roosmalen O S, Iachello F, Levine R D and Dieperink A E L 1983 J. Chem. Phys. 79 2515 Iachello F, Oss S and Lemus R 1991 J. Mol. Spectrosc. 146 56 van Roosmalen O S, Benjamin I and Levine R D 1984 J. Chem. Phys. 81 5986 Iachello F and Oss S 1990 J. Mol. Spectrosc. 142 85 [6] Iachello F, Oss S and Lemus R 1991 J. Mol. Spectrosc. 149 132 Iachello F, Manini N and Oss S 1992 J. Mol. Spectrosc. 156 190 Iachello F, Oss S and Viola L 1992 Mol. Phys. 78 545 Iachello F, Oss S and Viola L 1993 Mol. Phys. 78 561 [7] Lemus R and Frank A 1994 J. Chem. Phys. 101 8321 [8] Iachello F and Oss S 1992 J. Mol. Spectrosc. 153 225 Iachello F and Oss S 1993 Chem. Phys. Lett. 205 285 [9] Iachello F and Oss S 1991 Phys. Rev. Lett. 66 2976 Chen J Q, Iachello F and Ping J L 1996J. Chem. Phys. 104 815 [10] Marinkovic T and Oss S 2002 Phys. Chem. Comm. 5 66 [11] Marinkovic T and Oss S 2003 Phys. Chem. Comm. 6 42 [12] Oss S 2006 J. Mol. Struct. 780/781 87 [13] Iachello F and Oss S 2002 Eur. Phys. J. D 19 307 [14] Iachello F and Levine R D 1995 Algebraic Theory of Molecules (New York: Oxford University) [15] Frank A and van Isacker P 1994 Algebraic Methods in Molecular and Nuclear Structure Physics(New York: Wiley) [16] Oss S 1996 Adv. Chem. Phys. 93 455 [17] Sarkar N K , Choudhury J and Bhattacharjee R 2006 Mol. Phys. 104 3051 [18] Sarkar N K, Choudhury J and Bhattacharjee R 2008 Indian J. Phys. 82 767 [19] Sarkar N K, Choudhury J and Bhattacharje R 2007 Proceedings of the Asian Thermophysical Properties Conference (Fukuoka, Japan 2124 August 2007) paper 236 [20] Sarkar N K, Choudhury J, Karumuri S R and Bhattacharjee R 2008 Mol. Phys. 106 693 [21] Choudhury J, Karumuri S R, Sarkar N K and Bhattacharjee R 2008 Pramana J. Phys. 71 439 Choudhury J, Sarkar N K and Bhattacharjee R 2008 Indian J. Phys. 82 561 [22] Karumuri S R, Sarkar N K, Choudhury J and Bhattacharjee R 2008 Mol. Phys. 106 1733 Karumuri S R, Choudhury J, Sarkar N K and Bhattacharjee R 2008 J. Environmental Research and Development (to be published) Karumuri S R, Choudhury J , Sarkar N K and Bhattacharjee R 2008 Pramana J. Phys. (to be published) [23] Mills I M and Mompean F J 1986 Chem. Phys. Lett. 124 425 [24] L Halonen 1987.J. Chem. Phys. 86 3115 [25] Temsamani M A, Champion J M and Oss S 1999 J. Chem. Phys. 110 2893

All the values are in cm1 except which is dimensionless. In this study we have applied the one-dimensional algebraic model to C3 X4 (X=H, D) molecules. The algebraic Hamiltonian has been used to compute their energies up to second overtones. The stretching vibrational modes of C3 H4 and C3 D4 molecules are presented in Table 1. In the fundamental the splitting is 80.41 (CH), 104.55 (CD) for C3 H4 and C3 D4 molecules. The splitting pattern determines the nature of interbond interaction (our parameter = adj ). The present results show that (rms) = 16.42 and 16.71 cm1 for fundamentals of C3 X4 (X=H, D) molecules which is reasonable but becomes larger for rst overtones. The theoretical predicted (1 + 5 ) mode of C3 H4 molecule (deviation of 50.46 cm1 with the observed value) questions the experimental accuracy by this algebraic approach. The local versus normal behaviour of stretching modes of C3 X4 can be characterized by introduc[ ] ing the quantity, = 2/ arctan 8adj /( + ) . We nd = 0.4456 for CH bond and = 0.1635 for the

020308-3