Low-Temperature Photoelectron Spectroscopy of Aliphatic Dicarboxylate Monoanions, HO2C(CH2)nCO2-(n=1-10): Hydrogen Bond Induced Cyclization and Strain Energies
Journal Article
·
· Journal of Physical Chemistry A, 110(25):7801-7805
Photoelectron spectra of singly-charged dicarboxylate anions HO2C(CH2)nCO2 - (n = 1 – 10) are obtained at two different temperatures (300 and 70 K) at 193 nm. The electron binding energies of these species are observed to be much higher than the singly-charged monocarboxylate anions, suggesting the singly-charged dicarboxylate anions are cyclic due to strong intramolecular hydrogen bonding between the terminal –CO2H and –CO2 - groups. The measured electron binding energies are observed to depend on the chain length, reflecting the different –CO2H…-O2C– hydrogen bonding strength as a result of strain in the cyclic conformation. A minimum binding energy is found at n = 5, indicating that its intramolecular hydrogen bond is the weakest. At 70 K, all spectra are blue-shifted relative to the room temperature spectra with the maximum binding energy shift occurring at n = 5. These observations suggest that the cyclic conformation of HO2C(CH2)5CO2 - (a ten-membered ring) is the most strained among the ten anions. The present study shows that the –CO2H…-O2C– hydrogen bonding strength is different among the ten anions and it is very sensitive to the strain in the cyclic conformations.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 887368
- Report Number(s):
- PNNL-SA-49264; 3170a; KC0301020
- Journal Information:
- Journal of Physical Chemistry A, 110(25):7801-7805, Journal Name: Journal of Physical Chemistry A, 110(25):7801-7805 Journal Issue: 25 Vol. 110
- Country of Publication:
- United States
- Language:
- English
Similar Records
Photoelectron Imaging of Doubly Charged Anions, -O2C(CH2)nCO2- (n=2-8): Observation of Near 0 eV Electrons Due to Secondary Dissociative Autodetachment
Observation of Cysteine Thiolate and -S...H-O Intermolecular Hydrogen Bond
Observation of H-2 Aggregation onto a Doubly Charged Anion in a Temperature-Controlled Ion Trap
Journal Article
·
Wed Mar 17 00:00:00 EDT 2010
· Journal of Physical Chemistry A, 114(13):4524-4530
·
OSTI ID:982007
Observation of Cysteine Thiolate and -S...H-O Intermolecular Hydrogen Bond
Journal Article
·
Wed Nov 22 23:00:00 EST 2006
· Journal of Physical Chemistry A, 110(46):12603-12606
·
OSTI ID:918861
Observation of H-2 Aggregation onto a Doubly Charged Anion in a Temperature-Controlled Ion Trap
Journal Article
·
Wed Dec 24 23:00:00 EST 2008
· Journal of Physical Chemistry A, 112(51):13271-13274
·
OSTI ID:949937