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Filename: drivers/Session_files_driver.php
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File: /var/www/html/index.php
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Function: require_once
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Filename: Session/Session.php
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File: /var/www/html/index.php
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Function: require_once
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Filename: controllers/Detail.php
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File: /var/www/html/application/controllers/Detail.php
Line: 249
Function: _error_handler
File: /var/www/html/index.php
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Filename: controllers/Detail.php
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File: /var/www/html/application/controllers/Detail.php
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Function: _error_handler
File: /var/www/html/index.php
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Function: require_once
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Message: Trying to access array offset on value of type null
Filename: controllers/Detail.php
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File: /var/www/html/application/controllers/Detail.php
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Function: _error_handler
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Function: require_once
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Message: Trying to access array offset on value of type null
Filename: controllers/Detail.php
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Function: _error_handler
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Function: require_once
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Filename: models/Detail_model.php
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Function: strpos
File: /var/www/html/application/controllers/Detail.php
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Function: insertAPISummary
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Function: require_once
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Filename: helpers/my_audit_helper.php
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File: /var/www/html/application/helpers/my_audit_helper.php
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Function: str_replace
File: /var/www/html/application/controllers/Detail.php
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Function: formatAIDetailSummary
File: /var/www/html/index.php
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Function: require_once
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Filename: controllers/Detail.php
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Backtrace:
File: /var/www/html/application/controllers/Detail.php
Line: 256
Function: _error_handler
File: /var/www/html/index.php
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Function: require_once
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Message: Trying to access array offset on value of type null
Filename: controllers/Detail.php
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File: /var/www/html/application/controllers/Detail.php
Line: 256
Function: _error_handler
File: /var/www/html/index.php
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Function: require_once
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Message: Trying to access array offset on value of type null
Filename: controllers/Detail.php
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File: /var/www/html/application/controllers/Detail.php
Line: 256
Function: _error_handler
File: /var/www/html/index.php
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Function: require_once
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Message: Undefined array key "usage"
Filename: controllers/Detail.php
Line Number: 257
Backtrace:
File: /var/www/html/application/controllers/Detail.php
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Function: _error_handler
File: /var/www/html/index.php
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Message: Trying to access array offset on value of type null
Filename: controllers/Detail.php
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File: /var/www/html/application/controllers/Detail.php
Line: 257
Function: _error_handler
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Message: Undefined array key "usage"
Filename: controllers/Detail.php
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Function: _error_handler
File: /var/www/html/index.php
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Function: require_once
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Filename: controllers/Detail.php
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Function: _error_handler
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Filename: controllers/Detail.php
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Filename: controllers/Detail.php
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Filename: controllers/Detail.php
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Filename: controllers/Detail.php
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Function: _error_handler
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Message: file_get_contents(https://...@gmail.com&api_key=61f08fa0b96a73de8c900d749fcb997acc09): Failed to open stream: HTTP request failed! HTTP/1.1 429 Too Many Requests
Filename: helpers/my_audit_helper.php
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Function: file_get_contents
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Function: simplexml_load_file_from_url
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Function: pubMedGetRelatedKeyword
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Function: require_once
Unraveling dynamics of solvation and hydrogen bond (H-bond) reorganization between a solute and solvent is crucial to understand the importance of specific and nonspecific interactions in a solution-phase chemical reaction. Ultrafast time-resolved infrared (TRIR) spectroscopy provides direct opportunity to monitor site-specific intermolecular dynamics on a real-time scale by probing vibrational marker bands in the excited state of a solute. Herein, we report the real-time dynamics of vibrational cooling, solvation, and hydrogen bond reorganization of formylperylene (FPe) through TRIR spectroscopy of carbonyl (C═O) stretching mode in nonpolar, polar aprotic, and polar protic solvents. High sensitivity of the C═O stretch frequency (υ̅═) to photoinduced intramolecular charge transfer processes induced by specific and nonspecific solvent interactions led us to monitor the dynamics of dipolar solvation, site-specific H-bond formation, and reorganization processes by the TRIR method. In nonpolar cyclohexane, the υ̅═ stretch band appears at 1610 cm and exhibits negligible spectral shift over several tens of picoseconds. In acetonitrile, the υ̅═ peak shifts to 1594 cm and exhibits a further temporal red shift of about 5 cm with a characteristic solvation time scale of acetonitrile (τ ∼ 0.5 ps). In methanol, υ̅═ exhibits two bands corresponding to free and H-bonded FPe in early time scale. The free FPe population converts to the hydrogen-bonded population with a lifetime of about 10 ps. Vibrational cooling (τ ∼ 12-20 ps) in the excited electronic state of FPe could independently be monitored from the temporal dynamics of the ring vibration mode, which is less sensitive to solvation and hydrogen bonding. The present study provides insight into the specific and nonspecific solvation-controlled charge transfer dynamics in aprotic and protic solvents using FPe as a probe.
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Source |
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http://dx.doi.org/10.1021/acs.jpcb.9b01920 | DOI Listing |
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