The Other Side of NO; Nitric Oxide in the Infrared Jeremy Winick - AFRL retired M. G. Mlynczak - NASA Langley M. Lopez-Puertas - IAA R. Sharma - B.C. AFRL-AFGL Laboratory Group, CIRRIS-1A
Outline My journey - from LASP Post Doc to AFGL (AFRL) Nitric oxide infrared emission in Aurora - part AARC photochemical model of aurora CO2 NO, NO+ NO photochemical production NO(v) radiates in 5.3 m (fundamental) and 2.7 m (overtone). NO(v=1) efficiently excited atomic O thermospheric cooling Laboratory Measurements at AFGL CIRRIS 1A spectra non-equilibrium rotation and spinorbit populations Cooling and Energy Budget >13 years of TIMED/SABER data
My Journey through Career from LASP on Chemical Physics Ph.D 1976 Post Doc with Ian Stewart O3 SBUV AE, Photochemical Modeling O 3 Mars, SO2 Venus No work with Nitric Oxide 1982-2010 AFGL/AFRL first job photochemical auroral model (AARC) Included NO(v' v'-1, v'-2) emission Clever fast model ran on PC in 1985, stored efficiencies photons/ion pair for each vibrational transition) Our group Non-LTE expertise - worked on TIMED/SABER Science team (1998-2010)
Remote Sensing using IR Emission Available Day and Night High Resolution can provide Rotational temperature Kinetic temperature, Vib Temp Total population Low resolution/radiometry (SABER) need to Know what radiates in bandpass, derive temperature from multiple emitters, known mixing ratio Emission is related to radiative energy loss/cooling High Resolution (MIPAS - Lopez Puertas et al) measure NOx polar night descent O3 budget Can require complex instrumentation; cryo-cooling But SABER IS WORKING ON 14th YEAR
One of the first papers I read at AFGL
NO Properties and Production LASP familiar UV, especially the and bands IR - vibrational levels of the ground state. PCE Model NO(v 1) - production = loss, rad is 80 ms or less Chemiluminescent IR production: N(2D) + O2 NO(v,J) + O k1 5.7x10-12 cm3 s-1 N(4S) + O2 NO(v,J) + O k2 1.2x10-11exp(-3500/T) NO(v') + O NO(v'') + O VT - vibrationtranslation - Airglow Component NO(v') + h NO(v'-1;v'-2) Av'v'' Sets of vibrational level dependent quenching rates with [O], [O2] Before 1991 (CIRRIS 1A) assumed rotation and spin-orbit) were in thermal equilibrium
Lab Measurements - COCHISE (AFGL) Measure NO(v) distribution of N2D+O2 rxn from spectrum Doesn't directly yield v=0 Laser probing to get N2D and NO(v=0) populations Other reactants, flow, walls Not truly nascent distribution?
CIRRIS-1A Discoveries (B) High S/N, spectral resolution Subthermal spin-orbit states (A) High Rotation Bandheads (J (B,C) NO(1-0) near thermal rotation dominates (B) CO(1-0) 636 isotope also present (C) (C) (A)
Energy Budget Considerations: IR Cooling and Reduction in Heating Efficiency NO(v) Conventional IR Cooling: NO(v) a balance of V-T excitation and deexcitation NO(v') + M NO(v'') + M, M=[O] Most important v'=1, v''=0, 5.3 m Chemical heating reactions k1, k2 =3.8 and 1.39 ev (N+ O2) but some of that energy is lost by 5.3 m (less at 2.7 m) SABER measures a narrow bandpass, mostly on R-branch of fundamental Determining total NO radiated power, and what would be the NO(1-0) pure cooling rate requires modeling of components of the NO spectrum - involves unfilter factor Models done by Sharma and coworkers for non-equil NO(v,J) SABER NO radiated power acts as a thermostat (Mlynczak 2003) Responds on daily to solar cycle time scales
SABER NO - Solar Storm April 2002 April 19 April 14 Solar Storm NO Thermostat -S. Hemisphere April 16 - April 24, 2002
Nitric Oxide Cooling Increases in Disturbed Atmosphere - Thermostat NO cooling rate increase by more than 4x during the large solar storm of April 2002
SABER Radiated Power 2002-2014 NO Power CO2 Power Ap Index F10.7 cm Solar Flux
Summary NO infrared emission in the thermosphere is produced by Chemiluminescent chemical reactions Collisional excitation of NO(v=0), chiefly by atomic oxygen High resolution spectra show unusual rotational and spinorbit non-equilibrium as well as vibrational non-lte Still some uncertainty with regard to specific production rates Laboratory measurements of rates difficult, T-dep. Theoretical (quantum, semi-classical) calculations are difficult to quantify errors Limited field measurements with some uncertain background conditions NO 5.3 m radiation cools thermosphere 120 200km acts as a thermostat during disturbed conditions Further investigation with the newest atmospheric models could help resolve some issues.
References Armstrong et al., Highly rotationally Excited NO(v,J) in the thermosphere from CIRRIS 1A limb radiance measurements, GRL, 21, 2425, 1994. Caledonia and Kennealy, NO Infrared Radiation in the Upper Atmosphere, Planet. Space Sci., 30, 1043, 1982 Duff, Dothe, and Sharma, A first-principles model of spectrally resolved 5.3 m nitric oxide emission from aurorally dosed nighttime high-altitude terrestrial thermosphere, JGR, 2005GL023124. Funke et. al., Retrieval of stratospheric Nox from 5.3 and 6.2 mm non-lte by MIPAS, JGR, 110, 9302, 2005 Kockarts, Nitric Oxide Cooling in the Thermosphere, GRL, 7, 137, 1980 Lipson et al., Subthermal NO spin-orbit distributions in the Thermosphere, GRL, 21, 2421, 1994. Mlynczak et al., Observations of infrared radiative cooling in the thermosphere on daily to multiyear timescales from TIMED/SABER instrument, JGR 115, 115, A03309, 2010. Rawlins, Fraser, and Miller, Rovibrational Excitation of Nitric Oxide in the Reaction of O 2 with Metastable Atomic Nitrogen, J. Phys. Chem, 93, 1097, 1989 Sharma et al, Production of vibrationally and rotationally excited NO in the nighttime terrestrial atmosphere, JGR 101, 19707, 1996. Winick, et al., An Infrared Spectral Radiance Code for the Auroral Thermosphere (AARC), AFGL-TR-870334 (1987) - ADA202432 Winkler, Stachnik, Steinfeld, and Miller, Determination of NO(v=0-7) production from N 4S+O2 using 2photon ionization, J. Chem Phys 85(2), 890, 1986. Wise et al, Overview and summary of results and significant findings from CIRRIS-1A experiment, J. Spacecraft Rockets, 38, 297 (2001)
EXTRAS
Thermosphere Power Derivation from SABER Cooling Rate W m-3 Radiance Radiated Flux W m-2 Triennial Earth-Sun Summit, April 26-30, 2015 Daily Radiated Power (W)
SABER Daily Thermosphere NO Power (W) January 2002 September 2014 4620 Days of Data 5/14/15 Infrared Remote Sensing 17
SABER Daily Thermosphere NO Power (W) January 2002 September 2014 3.5 x 1018 more Joules annually 5/14/15 Infrared Remote Sensing 18
High Altitude NO Emission 66 to 77 N 55 to 66 N During storm time NO emission observed to over 280 km altitude 77 to 90 N Example above from Halloween storms of 2003 Signal levels imply NO ~ several percent VMR Data are unexplored at this altitude 5/14/15 Clemson University 19
Response to St. Patrick s Day 2015 Storm NO and CO2 combine to radiate about 42 billion kwh of Energy 5/14/15 Infrared Remote Sensing 20