Optical clocks at sea.

Deployed optical clocks will improve positioning for navigational autonomy1, provide remote time standards for geophysical monitoring2 and distributed coherent sensing3, allow time synchronization of remote quantum networks4,5 and provide operational redundancy for national time standards. Although laboratory optical clocks now reach fractional inaccuracies below 10-18 (refs. 6,7), transportable versions of these high-performing clocks8,9 have limited utility because of their size, environmental sensitivity and cost10. Here we report the development of optical clocks with the requisite combination of size, performance and environmental insensitivity for operation on mobile platforms. The 35 l clock combines a molecular iodine spectrometer, fibre frequency comb and control electronics. Three of these clocks operated continuously aboard a naval ship in the Pacific Ocean for 20 days while accruing timing errors below 300 ps per day. The clocks have comparable performance to active hydrogen masers in one-tenth the volume. Operating high-performance clocks at sea has been historically challenging and continues to be critical for navigation. This demonstration marks a significant technological advancement that heralds the arrival of future optical timekeeping networks.

Ultrafast oscilloscope based on laser-triggered field emitters.

Laser-triggered electron emission from sharp metal tips has been demonstrated in recent years as a high brightness, ultrafast electron source. Its possible applications range from ultrafast electron microscopy to laser-based particle accelerators to electron interferometry. The ultrafast nature of the emission process allows for the sampling of an instantaneous radio frequency (RF) voltage that has been applied to a field emitter. For proof-of-concept, we use an RF signal derived from our laser's repetition rate, mapping a 9.28 GHz signal in 22.4 fs steps with 28 mv accuracy.

Ultrafast Time-Resolved Photoelectric Emission.

The emission times of laser-triggered electrons from a sharp tungsten tip are directly characterized under ultrafast, near-infrared laser excitation at Keldysh parameters of 6.6<γ<19.1. Emission delays up to 10 fs are observed, which are inferred from the energy gain of photoelectrons emitted into a synchronously driven microwave cavity. Few femtosecond timing resolution is achieved in a configuration capable of measuring timing shifts up to 55 ps. The technique can also be used to measure the microwave phase inside the cavity with a precision below 70 fs upon the energy resolved detection of a single electron.

Excite-coupled trapping ring electrode cell (eTREC): radial trapping field control, linearized excitation, and improved detection.

A novel excite-coupled Trapping Ring Electrode Cell (eTREC) was designed and developed. eTREC technology provides greater linearity in the excitation electric field along with minimized variation in radial trapping field during detection. The variation in the radial trapping electric field is reduced through postexcitation modulation of the trapping potentials applied to the Trapping Ring Electrode Cell (TREC). Linearization of the electric field generated during radio frequency (RF) excitation is accomplished by coupling the RF excitation to a novel electrode arrangement superimposed onto the trapping rings of a TREC. The coupling of RF excitation to the trap plates effectively reduces z-axis ejection and allows for a more uniform postexcitation radius for the entire ion population. Using this technology, sensitivity was increased by >50%, resolution of (13)C(2) and (34)S fine structure peaks was achieved with the peptide MMMMG (approximately 330,000 RP) on a 3 T system, and the limit of detection was significantly reduced.

Trapping ring electrode cell: a FTICR mass spectrometer cell for improved signal-to-noise and resolving power.

A novel FTICR cell called the trapping ring electrode cell (TREC) has been conceived, simulated, developed, and tested. The performance of the TREC is compared to a closed cylindrical cell at different excited cyclotron radii. The TREC permits the ability to maintain coherent ion motion at larger initial excited cyclotron radii by decreasing the change in radial electric field with respect to z-axis position in the cell. This is accomplished through postexcitation modulation of the trapping potentials applied to segmented trap plates. Resolving power approaching the theoretical limit was achieved using the novel TREC technology; over 420,000 resolving power was observed on melittin [M + 4H] (4+) species when employed under modest magnetic field strength (3T) and a data acquisition duration of 13 s. A 10-fold gain in signal-to-noise ratio is demonstrated over the closed cylindrical cell optimized with common potentials on all ring electrodes. The observed frequency drift during signal acquisition over long time periods was also significantly reduced, resulting in improved resolving power.

A novel Fourier transform ion cyclotron resonance mass spectrometer with improved ion trapping and detection capabilities.

A novel Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer has been developed for improved biomolecule analysis. A flared metal capillary and an electrodynamic ion funnel were installed in the source region of the instrument for improved ion transmission. The transfer quadrupole is divided into 19 segments, with the capacity for independent control of DC voltage biases for each segment. Restrained ion population transfer (RIPT) is used to transfer ions from the ion accumulation region to the ICR cell. The RIPT ion guide reduces mass discrimination that occurs as a result of time-of-flight effects associated with gated trapping. Increasing the number of applied DC bias voltages from 8 to 18 increases the number of ions that are effectively trapped in the ICR cell. The RIPT ion guide with a novel voltage profile applied during ion transfer provides a 3- to 4-fold increase in the number of ions that are trapped in the ICR cell compared with gated trapping for the same ion accumulation time period. A novel ICR cell was incorporated in the instrument to reduce radial electric field variation for ions with different z-axis oscillation amplitudes. With the ICR cell, called trapping ring electrode cell (TREC), we can tailor the shape of the trapping electric fields to reduce dephasing of coherent cyclotron motion of an excited ion packet. With TREC, nearly an order of magnitude increase in sensitivity is observed. The performance of the instrument with the combination of RIPT, TREC, flared inlet, and ion funnel is presented.

Restrained ion population transfer: a novel ion transfer method for mass spectrometry.

Fourier transform ion cyclotron resonance (FTICR) mass spectrometers function such that the ion accumulation event takes place in a region of higher pressure outside the magnetic field which allows ions to be thermally cooled before being accelerated toward the ICR cell where they are decelerated and re-trapped. This transfer process suffers from mass discrimination due to time-of-flight effects. Also, trapping ions with substantial axial kinetic energy can decrease the performance of the FTICR instrument compared with the analysis of thermally cooled ions located at the trap center. Therefore, it is desirable to limit the energy imparted to the ions which results in lower applied trap plate potentials and reduces the spread in axial kinetic energy. The approach presented here for ion transfer, called restrained ion population transfer or RIPT, is designed to provide complete axial and radial containment of an ion population throughout the entire transfer process from the accumulation region to the ICR cell, eliminating mass discrimination associated with time-of-flight separation. This was accomplished by use of a number of quadrupole segments arranged in series with independent control of the direct current (DC) bias voltage applied to each segment of the quadrupole ion guide. The DC bias voltage is applied in such a way as to minimize the energy imparted to the ions allowing transfer of ions with low kinetic energy from the ion accumulation region to the ICR cell. Initial FTICR mass spectral data are presented that illustrate the feasibility of RIPT. A larger m/z range for a mixture of peptides is demonstrated compared with gated trapping. The increase in ion transfer time (3 ms to 130 ms) resulted in an approximately 11% decrease in the duty cycle; however this can be improved by simultaneously transferring multiple ion populations with RIPT. The technique was also modeled with SIMION 7.0 and simulation results that support our feasibility studies of the ion transfer process are presented.