Structure, Vibrational Spectra and Ring Puckering Barrier of Cyclobutane
We present the results of high level ab initio calculations on the structure and puckering barrier of cyclobutane in an effort to establish the minimum theoretical requirements needed for their accurate description. Our best computed value for the puckering angle is 29.68o. Furthermore we found that accurate estimates for the barrier between the minimum (D2d) and transition state (D4h) configurations require both higher levels of electron correlation [MP4, CCSD(T)] and basis sets of quadruple-z quality or larger. By performing CCSD(T) calculations with basis sets as large as cc-pV5Z we obtained a complete basis set (CBS) estimate of 498 cm-1 for the puckering barrier. Our estimate for the barrier is within 10 cm-1 to the value proposed originally, but it lies ~50 cm-1 higher than the one obtained more recently, therefore revisiting the analysis of the experimental data might be warranted. The results of the current study can serve as a guide for calculations on the substituted four member ring compounds. To this end we present a method for estimating the barrier height at higher levels of electron correlation [MP4, CCSD(T)] from the MP2 results.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 891108
- Report Number(s):
- PNNL-SA-36478; 17998; KC0301020; TRN: US200621%%5
- Journal Information:
- Journal of Physical Chemistry A, 110:10487-10494, Journal Name: Journal of Physical Chemistry A, 110:10487-10494
- Country of Publication:
- United States
- Language:
- English
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